Catalyst compositions and methods of making and using same

ABSTRACT

A catalyst composition comprising (i) a metal salt complex prepared from an imine phenol compound characterized by Structure 1: 
                         
wherein O and N represent oxygen and nitrogen respectively; R comprises a halogen, a hydrocarbyl group, or a substituted hydrocarbyl group; R 2  and R 3  are each independently hydrogen, a halogen, a hydrocarbyl group, or a substituted hydrocarbyl group; and Q is a donor group; and (ii) a metallocene complex.

CROSS REFERENCE TO RELATED APPLICATIONS

The subject matter of the present application is related to U.S. patentapplication Ser. No. 13/753,289 filed Jan. 29, 2013 and entitled “NovelPolymer Compositions and Methods of Making and Using Same,” which ishereby incorporated herein by reference in its entirety for allpurposes.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND

The present disclosure generally relates to catalyst systems and polymercompositions. Particularly, the present disclosure relates to novelcatalyst compositions for the production of multimodal polymer resins.

FIELD

Polyolefins are plastic materials useful for making a wide variety ofvalued products due to their combination of features such as stiffness,ductility, barrier properties, temperature resistance, opticalproperties, availability, and low cost. In particular, polyethylene (PE)is one of the largest volume polymers consumed in the world. It is aversatile polymer that offers high performance relative to otherpolymers and alternative materials such as glass or metal.

Multimodal PE resins offer the potential for broad applicability asthese resins can couple desirable physical properties and processingcharacteristics. There exists an ongoing need for improved catalystsystems for the production of polymeric compositions.

BRIEF SUMMARY

Disclosed herein is a catalyst composition comprising (i) a metal saltcomplex prepared from an imine phenol compound characterized byStructure I:

wherein O and N represent oxygen and nitrogen respectively; R comprisesa halogen, a hydrocarbyl group, or a substituted hydrocarbyl group; R²and R³ are each independently hydrogen, a halogen, a hydrocarbyl group,or a substituted hydrocarbyl group; and Q is a donor group; and (ii) ametallocene complex.

Also disclosed herein is a method comprising contacting a catalystcomposition with a monomer under conditions suitable for the formationof a polymer wherein the catalyst composition comprises a metal saltcomplex of an imine bis(phenolate) compound, a metallocene complex, asolid oxide, and an optional metal alkyl and wherein the metal saltcomplex of an imine bis(phenolate) compound comprises a compound havingStructure XIV

where M is titanium, zirconium, or hafnium; Et₂O is optional; Rcomprises a halogen, a hydrocarbyl group, or a substituted hydrocarbylgroup; and R² comprises hydrogen, a halogen, a hydrocarbyl group, or asubstituted hydrocarbyl group.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a representative tensile stress-strain curve.

FIG. 2 is a gel permeation chromatograph of the samples from theexample.

FIG. 3 is a plot of the dynamic melt viscosity as a function offrequency for the samples from the example.

FIGS. 4 and 5 are plots of the short chain branching distribution forthe samples from the example.

DETAILED DESCRIPTION

Disclosed herein are novel catalyst and polymer compositions and methodsof making and using same. In an embodiment, the catalyst compositioncomprises a mixture of a metal-salt complex prepared from an iminephenol compound and at least one metallocene-containing compound and isdesignated herein as CATCOMP. CATCOMPs may be utilized in the productionof multimodal polymer compositions displaying both desirable performanceand processing properties. These aspects of this disclosure are furtherdescribed herein.

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Groups of elements of the table are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances agroup of elements may be indicated using a common name assigned to thegroup; for example alkali earth metals (or alkali metals) for Group 1elements, alkaline earth metals (or alkaline metals) for Group 2elements, transition metals for Group 3-12 elements, and halogens forGroup 17 elements.

A chemical “group” is described according to how that group is formallyderived from a reference or “parent” compound, for example, by thenumber of hydrogen atoms formally removed from the parent compound togenerate the group, even if that group is not literally synthesized inthis manner. These groups can be utilized as substituents or coordinatedor bonded to metal atoms. By way of example, an “alkyl group” formallycan be derived by removing one hydrogen atom from an alkane, while an“alkylene group” formally can be derived by removing two hydrogen atomsfrom an alkane. Moreover, a more general term can be used to encompass avariety of groups that formally are derived by removing any number (“oneor more”) hydrogen atoms from a parent compound, which in this examplecan be described as an “alkane group,” and which encompasses an “alkylgroup,” an “alkylene group,” and materials have three or more hydrogensatoms, as necessary for the situation, removed from the alkane.Throughout, the disclosure that a substituent, ligand, or other chemicalmoiety may constitute a particular “group” implies that the well-knownrules of chemical structure and bonding are followed when that group isemployed as described. When describing a group as being “derived by,”“derived from,” “formed by,” or “formed from,” such terms are used in aformal sense and are not intended to reflect any specific syntheticmethods or procedure, unless specified otherwise or the context requiresotherwise.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups mayalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.“Substituted” is intended to be non-limiting and include inorganicsubstituents or organic substituents.

Unless otherwise specified, any carbon-containing group for which thenumber of carbon atoms is not specified can have, according to properchemical practice, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbonatoms, or any range or combination of ranges between these values. Forexample, unless otherwise specified, any carbon-containing group canhave from 1 to 30 carbon atoms, from 1 to 25 carbon atoms, from 1 to 20carbon atoms, from 1 to 15 carbon atoms, from 1 to 10 carbon atoms, orfrom 1 to 5 carbon atoms, and the like. Moreover, other identifiers orqualifying terms may be utilized to indicate the presence or absence ofa particular substituent, a particular regiochemistry and/orstereochemistry, or the presence or absence of a branched underlyingstructure or backbone.

The term “organyl group” is used herein in accordance with thedefinition specified by IUPAC: an organic substituent group, regardlessof functional type, having one free valence at a carbon atom. Similarly,an “organylene group” refers to an organic group, regardless offunctional type, derived by removing two hydrogen atoms from an organiccompound, either two hydrogen atoms from one carbon atom or one hydrogenatom from each of two different carbon atoms. An “organic group” refersto a generalized group formed by removing one or more hydrogen atomsfrom carbon atoms of an organic compound. Thus, an “organyl group,” an“organylene group,” and an “organic group” can contain organicfunctional group(s) and/or atom(s) other than carbon and hydrogen, thatis, an organic group can comprise functional groups and/or atoms inaddition to carbon and hydrogen. For instance, non-limiting examples ofatoms other than carbon and hydrogen include halogens, oxygen, nitrogen,phosphorus, and the like. Non-limiting examples of functional groupsinclude ethers, aldehydes, ketones, esters, sulfides, amines,phosphines, and so forth. In one aspect, the hydrogen atom(s) removed toform the “organyl group,” “organylene group,” or “organic group” may beattached to a carbon atom belonging to a functional group, for example,an acyl group (—C(O)R), a formyl group (—C(O)H), a carboxy group(—C(O)OH), a hydrocarboxycarbonyl group (—C(O)OR), a cyano group (—C≡N),a carbamoyl group (—C(O)NH₂), an N-hydrocarbylcarbamoyl group(—C(O)NHR), or N,N′-dihydrocarbylcarbamoyl group (—C(O)NR₂), among otherpossibilities. In another aspect, the hydrogen atom(s) removed to formthe “organyl group,” “organylene group,” or “organic group” may beattached to a carbon atom not belonging to, and remote from, afunctional group, for example, —CH₂C(O)CH₃, —CH₂NR₂, and the like. An“organyl group,” “organylene group,” or “organic group” may bealiphatic, inclusive of being cyclic or acyclic, or may be aromatic.“Organyl groups,” “organylene groups,” and “organic groups” alsoencompass heteroatom-containing rings, heteroatom-containing ringsystems, heteroaromatic rings, and heteroaromatic ring systems. “Organylgroups,” “organylene groups,” and “organic groups” may be linear orbranched unless otherwise specified. Finally, it is noted that the“organyl group,” “organylene group,” or “organic group” definitionsinclude “hydrocarbyl group,” “hydrocarbylene group,” “hydrocarbongroup,” respectively, and “alkyl group,” “alkylene group,” and “alkanegroup,” respectively, as members.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.halogenated alkane indicates that the presence of one or more halogenatoms replacing an equivalent number of hydrogen atoms in the alkane).The term “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic groups, and/or may be linearor branched unless otherwise specified. Primary, secondary, and tertiaryalkyl group are derived by removal of a hydrogen atom from a primary,secondary, tertiary carbon atom, respectively, of an alkane. The n-alkylgroup may be derived by removal of a hydrogen atom from a terminalcarbon atom of a linear alkane. The groups RCH₂ (R≠H), R₂CH (R≠H), andR₃C (R≠H) are primary, secondary, and tertiary alkyl groups,respectively.

A “halide” has its usual meaning; therefore, examples of halides includefluoride, chloride, bromide, and iodide.

Within this disclosure the normal rules of organic nomenclature willprevail. For instance, when referencing substituted compounds or groups,references to substitution patterns are taken to indicate that theindicated group(s) is (are) located at the indicated position and thatall other non-indicated positions are hydrogen. For example, referenceto a 4-substituted phenyl group indicates that there is a non-hydrogensubstituent located at the 4 position and hydrogens located at the 2, 3,5, and 6 positions. By way of another example, reference to a3-substituted naphth-2-yl indicates that there is a non-hydrogensubstituent located at the 3 position and hydrogens located at the 1, 4,5, 6, 7, and 8 positions. References to compounds or groups havingsubstitutions at positions in addition to the indicated position will bereference using comprising or some other alternative language. Forexample, a reference to a phenyl group comprising a substituent at the 4position refers to a group having a non-hydrogen atom at the 4 positionand hydrogen or any non-hydrogen group at the 2, 3, 5, and 6 positions.

Embodiments disclosed herein the may provide the materials listed assuitable for satisfying a particular feature of the embodiment delimitedby the term “or.” For example, a particular feature of the subjectmatter may be disclosed as follows: Feature X can be A, B, or C. It isalso contemplated that for each feature the statement can also bephrased as a listing of alternatives such that the statement “Feature Xis A, alternatively B, or alternatively C” is also an embodiment of thepresent disclosure whether or not the statement is explicitly recited.

In an embodiment, the imine phenol compound is characterized byStructure I:

where O and N represent oxygen and nitrogen respectively and Qrepresents a donor group. One or more of R, R², and R³, may each be thesame or different and may be selected from the embodiments describedherein. R can be a halogen, a hydrocarbyl group, or a substitutedhydrocarbyl group. In an embodiment, R is not hydrogen. R² and R³ caneach independently be hydrogen, a halogen, a hydrocarbyl group, or asubstituted hydrocarbyl group. These substituents are described in moredetail herein.

Referring to Structure I, generally, R, R² and R³ can each independentlybe a hydrocarbyl group. In an embodiment, R, R² and R³ can eachindependently be a C₁ to C₃₀ hydrocarbyl group; a C₁ to C₂₀ hydrocarbylgroup; a C₁ to C₁₅ hydrocarbyl group; a C₁ to C₁₀ hydrocarbyl group; ora C₁ to C₅ hydrocarbyl group. In yet other embodiments, R, R² and R³ caneach independently be a C₃ to C₃₀ aromatic group; a C₃ to C₂₀ aromaticgroup; a C₃ to C₁₅ aromatic group; or a C₃ to C₁₀ aromatic group.

In an aspect, R, R² and R³ can each independently be a C₁ to C₃₀ alkylgroup, a C₄ to C₃₀ cycloalkyl group, a C₄ to C₃₀ substituted cycloalkylgroup, a C₃ to C₃₀ aliphatic heterocyclic group, a C₃ to C₃₀ substitutedaliphatic heterocyclic group, a C₆ to C₃₀ aryl group, a C₆ to C₃₀substituted aryl group, a C₇ to C₃₀ aralkyl group, a C₇ to C₃₀substituted aralkyl group, a C₃ to C₃₀ heteroaryl group, or a C₃ to C₃₀substituted heteroaryl group. In an embodiment, R, R² and R³ can eachindependently be a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group,a C₄ to C₂₀ substituted cycloalkyl group, a C₃ to C₂₀ aliphaticheterocyclic group, a C₃ to C₂₀ substituted aliphatic heterocyclicgroup, a C₆ to C₂₀ aryl group, a C₆ to C₂₀ substituted aryl group, a C₇to C₂₀ aralkyl group, a C₇ to C₂₀ substituted aralkyl group, a C₃ to C₂₀heteroaryl group, or a C₃ to C₂₀ substituted heteroaryl group. In otherembodiments, R, R² and R³ can each independently be a C₁ to C₁₀ alkylgroup, a C₄ to C₁₅ cycloalkyl group, a C₄ to C₁₅ substituted cycloalkylgroup, a C₃ to C₁₅ aliphatic heterocyclic group, a C₃ to C₁₅ substitutedaliphatic heterocyclic group, a C₆ to C₁₅ aryl group, a C₆ to C₁₅substituted aryl group, a C₇ to C₁₅ aralkyl group, a C₇ to C₁₅substituted aralkyl group, a C₃ to C₁₅ heteroaryl group, or a C₃ to C₁₅substituted heteroaryl group. In further embodiments, R, R² and R³ caneach independently be C₁ to C₅ alkyl group.

In an embodiment, R, R² and R³ can each independently be a methyl group,an ethyl group, a propyl group, a butyl group, a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group, anundecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, apentadecyl group, a hexadecyl group, a heptadecyl group, an octadecylgroup, or a nonadecyl group. In some embodiments, the alkyl groups whichcan be utilized as R, R² and R³ can each independently be substituted.Each substituent of a substituted alkyl group independently can be ahalogen or a hydrocarboxy group; alternatively, a halogen; oralternatively, a hydrocarboxy group. Halogens and hydrocarboxy groupsthat can be utilized as substituents are independently disclosed hereinand can be utilized without limitation to further describe thesubstituted alkyl group which can be utilized as R, R² and/or R³.

In an embodiment, R, R² and R³ can each independently be a cyclobutylgroup, a substituted cyclobutyl group, a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, a substitutedcyclohexyl group, a cycloheptyl group, a substituted cycloheptyl group,a cyclooctyl group, or a substituted cyclooctyl group. In someembodiments, R, R² and R³ can each independently be a cyclopentyl group,a substituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group.

In an embodiment, each substituent for a substituted cycloalkyl group(general or specific) that can be utilized as R, R² and R³ can eachindependently be a halogen, a hydrocarbyl group, or a hydrocarboxygroup. In some embodiments, each substituent for a substitutedcycloalkyl group (general or specific) that can be utilized as R, R² andR³ can each independently be a halogen, an alkyl group, or an alkoxygroup. Halogens, hydrocarbyl groups, hydrocarboxy groups, alkyl group,and alkoxy groups that can be utilized as substituents are independentlydisclosed herein and can be utilized without limitation to furtherdescribe the substituents for a substituted cycloalkyl group (general orspecific) that can be utilized as R, R² and/or R³.

In an aspect, R, R² and R³ can each independently have Structure II:

wherein the undesignated valency (*) represents the point at which thesubstituent (i.e., R, R² or R³) attaches to the transition-metal saltcomplex of Structure I. Generally, R^(21c), R^(23c), R^(24c), andR^(25c) independently can be hydrogen or a non-hydrogen substituent, andn can be an integer from 1 to 5.

In an embodiment wherein R, R² and R³ has Structure II, R^(21c),R^(23c), R^(24c), and R^(25c) can be hydrogen and R^(22c) can be anynon-hydrogen substituent disclosed herein; or alternatively, R^(21c),R^(23c), and R^(25c) can be hydrogen and R^(22c) and R^(24c)independently can be any non-hydrogen substituent disclosed herein. Inan embodiment, n can be an integer from 1 to 4; or alternatively, from 2to 4. In other embodiments, n can be 2 or 3; alternatively, 2; oralternatively, 3.

In an embodiment, R^(21c), R^(22c), R^(23c), R^(24c), and R^(25c)independently can be hydrogen, a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, hydrogen, a halogen, or a hydrocarbylgroup. In some embodiments, R^(21c), R^(22c), R^(23c), R^(24c), andR^(25c) independently can be hydrogen, a halogen, an alkyl group, or analkoxy group. Halogens, hydrocarbyl groups, hydrocarboxy groups, alkylgroup, and alkoxy groups that can be utilized as substituents areindependently disclosed herein and can be utilized without limitation tofurther describe the R, R² or R³ group having Structure II.

In an embodiment, R, R² and R³ can each independently be a phenyl groupor a substituted phenyl group. In an embodiment, the substituted phenylgroup can be a 2-substituted phenyl group, a 3-substituted phenyl group,a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group.

In an embodiment, each substituent for a substituted phenyl groupindependently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup. In some embodiments, each substituent for a substituted phenylgroup independently can be a halogen, an alkyl group, or an alkoxygroup. Halogens, hydrocarbyl groups, hydrocarboxy groups, alkyl groups,and alkoxy groups that can be utilized as substituents are independentlydisclosed herein and can be utilized without limitation to furtherdescribe the substituents for the substituted phenyl group.

In an aspect, R, R² and R³ can each independently have Structure III:

wherein the undesignated valency (*) represents the point at which thesubstituent (i.e., R, R² or R³) attaches to the transition-metal saltcomplex of Structure I. Generally, R²², R²³, R²⁴, R²⁵, and R²⁶independently can be hydrogen or a non-hydrogen substituent. In anembodiment wherein R, R² or R³ has Structure III, R²², R²³, R²⁴, R²⁵,and R²⁶ can be hydrogen, R²³, R²⁴, R²⁵, and R²⁶ can be hydrogen and R²²can be a non-hydrogen substituent, R²², R²⁴, R²⁵, and R²⁶ can behydrogen and R²³ can be a non-hydrogen substituent, R²², R²³, R²⁵, andR²⁶ can be hydrogen and R²⁴ can be a non-hydrogen substituent, R²³, R²⁵,and R²⁶ can be hydrogen and R²² and R²⁴ can be non-hydrogensubstituents, R²³, R²⁴, and R²⁵ can be hydrogen and R²² and R²⁶ can benon-hydrogen substituents, R²², R²⁴, and R²⁶ can be hydrogen and R²³ andR²⁵ can be non-hydrogen substituents, or R²³ and R²⁵ can be hydrogen andR²², R²⁴, and R²⁶ can be non-hydrogen substituents. In some embodimentswherein R, R² or R³ has Structure III, R²³, R²⁴, R²⁵, and R²⁶ can behydrogen and R²² can be a non-hydrogen substituent, R²², R²³, R²⁵, andR²⁶ can be hydrogen and R²⁴ can be a non-hydrogen substituent, R²³, R²⁵,and R²⁶ can be hydrogen and R²² and R²⁴ can be non-hydrogensubstituents, R²³, R²⁴, and R²⁵ can be hydrogen and R²² and R²⁶ can benon-hydrogen substituents, or R²³ and R²⁵ can be hydrogen and R²², R²⁴,and R²⁶ can be non-hydrogen substituents; alternatively, R²³, R²⁴, R²⁵,and R²⁶ can be hydrogen and R²² can be a non-hydrogen substituent, R²²,R²³, R²⁵, and R²⁶ can be hydrogen and R²⁴ can be a non-hydrogensubstituent, R²³, R²⁵, and R²⁶ can be hydrogen and R²² and R²⁴ can benon-hydrogen substituents, or R²³, R²⁴, and R²⁵ can be hydrogen and R²²and R²⁶ can be non-hydrogen substituents; alternatively, R²², R²⁴, R²⁵,and R²⁶ can be hydrogen and R²³ can be a non-hydrogen substituent, orR²², R²⁴, and R²⁶ can be hydrogen and R²³ and R²⁵ can be non-hydrogensubstituents; alternatively, R²³, R²⁴, R²⁵, and R²⁶ can be hydrogen andR²² can be a non-hydrogen substituent, or R²², R²³, R²⁵, and R²⁶ can behydrogen and R²⁴ can be a non-hydrogen substituent; alternatively, R²³,R²⁵, and R²⁶ can be hydrogen and R²² and R²⁴ can be non-hydrogensubstituents, R²³, R²⁴, and R²⁵ can be hydrogen and R²² and R²⁶ can benon-hydrogen substituents, or R²³ and R²⁵ can be hydrogen and R²², R²⁴,and R²⁶ can be non-hydrogen substituents; or alternatively, R²³, R²⁵,and R²⁶ can be hydrogen and R²² and R²⁴ can be non-hydrogensubstituents, or R²³, R²⁴, and R²⁵ can be hydrogen and R²² and R²⁶ canbe non-hydrogen substituents. In other embodiments wherein R, R² or R³has Structure III, R²², R²³, R²⁴, R²⁵, and R²⁶ can be hydrogen;alternatively, R²³, R²⁴, R²⁵, and R²⁶ can be hydrogen and R²² can be anon-hydrogen substituent; alternatively, R²², R²⁴, R²⁵, and R²⁶ can behydrogen and R²³ can be a non-hydrogen substituent; alternatively, R²²,R²³, R²⁵, and R²⁶ can be hydrogen and R²⁴ can be a non-hydrogensubstituent; alternatively, R²³, R²⁵, and R²⁶ can be hydrogen and R²²and R²⁴ can be non-hydrogen substituents; alternatively, R²³, R²⁴, andR²⁵ can be hydrogen and R²² and R²⁶ can be non-hydrogen substituents;alternatively, R²², R²⁴, and R²⁶ can be hydrogen and R²³ and R²⁵ and canbe non-hydrogen substituents; or alternatively, R²³ and R²⁵ can behydrogen and R²², R²⁴, and R²⁶ can be non-hydrogen substituents.

In an embodiment, the non-hydrogen substituents that can be utilized asR²², R²³, R²⁴, R²⁵, and R²⁶ in the R, R² or R³ group having StructureIII independently can be a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, a halogen or a hydrocarbyl group. Insome embodiments, the non-hydrogen substituents that can be utilized asR²², R²³, R²⁴, R²⁵, and R²⁶ in the R, R² or R³ group having StructureIII independently can be a halogen, an alkyl group, or an alkoxy group.Halogens, hydrocarbyl groups, hydrocarboxy groups, alkyl groups, andalkoxy groups that can be utilized as substituents are independentlydisclosed herein and can be utilized without limitation to furtherdescribe the R, R² and/or R³ group having Structure III.

In an aspect, R, R² and R³ can each independently be a benzyl group, asubstituted benzyl group, a 1-phenyleth-1-yl group, a substituted1-phenyleth-1-yl, a 2-phenyleth-1-yl group, or a substituted2-phenyleth-1-yl group. In an embodiment, R, R² and R³ can eachindependently be a benzyl group, or a substituted benzyl group;alternatively, a 1-phenyleth-1-yl group or a substituted1-phenyleth-1-yl; alternatively, a 2-phenyleth-1-yl group or asubstituted 2-phenyleth-1-yl group; or alternatively, a benzyl group, a1-phenyleth-1-yl group, or a 2-phenyleth-1-yl group. In someembodiments, R, R² and R³ can each independently be a benzyl group;alternatively, a substituted benzyl group; alternatively, a1-phenyleth-1-yl group; alternatively, a substituted 1-phenyleth-1-yl;alternatively, a 2-phenyleth-1-yl group; or alternatively, a substituted2-phenyleth-1-yl group.

In an embodiment, each substituent for a substituted benzyl group, a1-phenyleth-1-yl group, or a 2-phenyleth-1-yl group (general orspecific) that can be utilized as R, R² and/or R³ can be a halogen, ahydrocarbyl group, or a hydrocarboxy group. In some embodiments, eachsubstituent for a substituted benzyl group, 1-phenyleth-1-yl group, or a2-phenyleth-1-yl group (general or specific) that can be utilized as R,R² and/or R³ independently can be halogen, an alkyl group, or an alkoxygroup. Halogens, hydrocarbyl groups, hydrocarboxy groups, alkyl groups,and alkoxy groups that can be utilized as substituents are independentlydisclosed herein and can be utilized without limitation to furtherdescribe the substituents for the substituted benzyl group,1-phenyleth-1-yl group, or a 2-phenyleth-1-yl group (general orspecific) that can be utilized as R, R² and/or R³.

In an aspect, R, R² and R³ can each independently be a pyridinyl group,a substituted pyridinyl group, a furyl group, a substituted furyl group,a thienyl group, or a substituted thienyl group.

In an embodiment, the pyridinyl (or substituted pyridinyl) R, R² and/orR³ can be a pyridin-2-yl group, a substituted pyridin-2-yl group, apyridin-3-yl group, a substituted pyridin-3-yl group, a pyridin-4-ylgroup, or a substituted pyridin-4-yl group; alternatively, apyridin-2-yl group, a pyridin-3-yl group, or a pyridin-4-yl group. Insome embodiments, the pyridinyl (or substituted pyridinyl) R, R² and/orR³ group can be a pyridin-2-yl group or a substituted pyridin-2-ylgroup; alternatively, a pyridin-3-yl group or a substituted pyridin-3-ylgroup; alternatively, a pyridin-4-yl group or a substituted pyridin-4-ylgroup; alternatively, a pyridin-2-yl group; alternatively, a substitutedpyridin-2-yl group; alternatively, a pyridin-3-yl group; alternatively,a substituted pyridin-3-yl group; alternatively, a pyridin-4-yl group;or alternatively, a substituted pyridin-4-yl group. In an embodiment,the substituted pyridinyl R, R² and/or R³ group can be a 2-substitutedpyridin-3-yl group, a 4-substituted pyridin-3-yl group, a 5-substitutedpyridin-3-yl group, a 6-substituted pyridin-3-yl group, a2,4-disubstituted pyridin-3-yl group, a 2,6-disubstituted pyridin-3-ylgroup, or a 2,4,6-trisubstituted pyridin-3-yl group; alternatively, a2-substituted pyridin-3-yl group, a 4-substituted pyridin-3-yl group, ora 6-substituted pyridin-3-yl group; alternatively, a 2,4-disubstitutedpyridin-3-yl group or a 2,6-disubstituted pyridin-3-yl group;alternatively, a 2-substituted pyridin-3-yl group; alternatively, a4-substituted pyridin-3-yl group; alternatively, a 5-substitutedpyridin-3-yl group; alternatively, a 6-substituted pyridin-3-yl group;alternatively, a 2,4-disubstituted pyridin-3-yl group; alternatively, a2,6-disubstituted pyridin-3-yl group; or alternatively, a2,4,6-trisubstituted pyridin-3-yl group.

In an embodiment, the furyl (or substituted furyl) R, R² and/or R³ groupcan be a fur-2-yl group, a substituted fur-2-yl group, a fur-3-yl group,or a substituted fur-3-yl group. In an embodiment, the substituted furylR, R² and/or R³ group can be a 2-substituted fur-3-yl group, a4-substituted fur-3-yl group, or a 2,4-disubstituted fur-3-yl group.

In an embodiment, the thienyl (or substituted thienyl) R, R² and/or R³group can be a thien-2-yl group, a substituted thien-2-yl group, athien-3-yl group, or a substituted thien-3-yl group. In someembodiments, the thienyl (or substituted thienyl) R, R² and/or R³ groupcan be a thien-2-yl group or a substituted thien-2-yl group. In anembodiment, the substituted thienyl R, R² and/or R³ group can be a2-substituted thien-3-yl group, a 4-substituted thien-3-yl group, or a2,4-disubstituted thien-3-yl group.

In an embodiment, each substituent for a substituted pyridinyl, furyl,or thienyl groups (general or specific) that can be utilized as R, R²and/or R³ can each independently be a halogen, a hydrocarbyl group, or ahydrocarboxy group. In some embodiments, each substituent for asubstituted pyridinyl, furyl, and/or or thienyl group (general orspecific) that can be utilized as R, R² and R³ each independently can bea halogen, an alkyl group, or an alkoxy group; alternatively, a halogenor an alkyl group; alternatively, a halogen or an alkoxy group;alternatively, an alkyl group or an alkoxy group; alternatively, ahalogen; alternatively, an alkyl group; or alternatively, an alkoxygroup. Halogens, hydrocarbyl groups, hydrocarboxy groups, alkyl groups,and alkoxy groups that can be utilized as substituents are independentlydisclosed herein and can be utilized without limitation to furtherdescribe the substituents for the substituted pyridinyl, furyl, and/orthienyl groups (general or specific) that can be utilized as R, R²and/or R³.

In a non-limiting embodiment, R, R² and/or R³ can each independently bea phenyl group, a 2-alkylphenyl group, a 3-alkylphenyl group, a4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, a 3,5-dialkylphenyl group, or a 2,4,6-trialkylphenyl group;alternatively, a 2-alkylphenyl group, a 4-alkylphenyl group, a2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a2,4,6-trialkylphenyl group. In another non-limiting embodiment, R, R²and R³ can each independently be a phenyl group, a 2-alkoxyphenyl group,a 3-alkoxyphenyl group, a 4-alkoxyphenyl group, or 3,5-dialkoxyphenylgroup. In other non-limiting embodiments, R, R² and R³ can eachindependently be a phenyl group, a 2-halophenyl group, a 3-halophenylgroup, a 4-halophenyl group, a 2,6-dihalophenyl group, or a3,5-dialkylphenyl group; alternatively, a 2-halophenyl group, a4-halophenyl group, or a 2,6-dihalophenyl group; alternatively, a2-halophenyl group or a 4-halophenyl group; alternatively, a3-halophenyl group or a 3,5-dihalophenyl group; alternatively, a2-halophenyl group; alternatively, a 3-halophenyl group; alternatively,a 4-halophenyl group; alternatively, a 2,6-dihalophenyl group; oralternatively, a 3,5-dihalophenyl group. Halides, alkyl groupsubstituents, and alkoxy group substituents are independently describedherein and can be utilized, without limitation, to further describe thealkylphenyl, dialkylphenyl, trialkylphenyl, alkoxyphenyl,dialkoxyphenyl, halophenyl, or dihalophenyl groups that can be utilizedfor R, R² and/or R³. Generally, the halides, alkyl substituents, oralkoxy substituents of a dialkyl, trialkyl phenyl, dialkoxyphenyl, ordihalophenyl groups can be the same; or alternatively, the halo, alkylsubstituents, or alkoxy substituents of alkylphenyl, dialkylphenyl,trialkylphenyl, dialkoxyphenyl, or dihalophenyl groups can be different.

In a non-limiting embodiment, R, R² and R³ can each independently be a2-methylphenyl group, a 2-ethylphenyl group, a 2-isopropylphenyl group,a 2-tert-butylphenyl group, a 4-methylphenyl group, a 4-ethylphenylgroup, a 4-isopropylphenyl group, or a 4-tert-butylphenyl group;alternatively, a 2-methylphenyl group, a 2-ethylphenyl group, a2-isopropylphenyl group, or a 2-tert-butylphenyl group; alternatively, a4-methylphenyl group, a 4-ethylphenyl group, a 4-isopropylphenyl group,or a 4-tert-butylphenyl group; alternatively, a 2-methylphenyl group;alternatively, a 2-ethylphenyl group; alternatively, a 2-isopropylphenylgroup; alternatively, a 2-tert-butylphenyl group; alternatively, a4-methylphenyl group; alternatively, a 4-ethylphenyl group;alternatively, a 4-isopropylphenyl group; or alternatively, a4-tert-butylphenyl group. In another non-limiting embodiment, R, R² andR³ can each independently be a 2-methoxyphenyl group, a 2-ethoxyphenylgroup, a 2-isopropoxyphenyl group, a 2-tert-butoxyphenyl group, a4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenylgroup, or a 4-tert-butoxyphenyl group; alternatively, a 2-methoxyphenylgroup, a 2-ethoxyphenyl group, a 2-isopropoxyphenyl group, or a2-tert-butoxyphenyl group; alternatively, a 4-methoxyphenyl group, a4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a4-tert-butoxyphenyl group; alternatively, a 2-methoxyphenyl group;alternatively, a 2-ethoxyphenyl group; alternatively, a2-isopropoxyphenyl group; alternatively, a 2-tert-butoxyphenyl group;alternatively, a 4-methoxyphenyl group; alternatively, a 4-ethoxyphenylgroup; alternatively, a 4-isopropoxyphenyl group; or alternatively, a4-tert-butoxyphenyl group. In other non-limiting embodiments, R, R² andR³ can each independently be a 2-fluorophenyl group, a 2-chlorophenylgroup, a 3-fluorophenyl group, a 3-chlorophenyl group, a 4-fluorophenylgroup, a 4-chlorophenyl group, a 3,5-difluorophenyl group, or a3,5-dichlorophenyl group; alternatively, a 2-fluorophenyl group or a2-chlorophenyl group; alternatively, a 3-fluorophenyl group or a3-chlorophenyl group; alternatively, a 4-fluorophenyl group or a4-chlorophenyl group; alternatively, a 3,5-difluorophenyl group or a3,5-dichlorophenyl group; alternatively, a 3-fluorophenyl group, a3-chlorophenyl group, a 3,5-difluorophenyl group or a 3,5-dichlorophenylgroup; alternatively, a 3-fluorophenyl group or a 3,5-difluorophenylgroup; alternatively, a 2-fluorophenyl group; alternatively, a2-chlorophenyl group; alternatively, a 3-fluorophenyl group;alternatively, a 3-chlorophenyl group; alternatively, a 4-fluorophenylgroup; alternatively, a 4-chlorophenyl; alternatively, a3,5-difluorophenyl group; or alternatively, a 3,5-dichlorophenyl group.

In an embodiment, Q is a donor group which can have Structure (II),(III) or (IV):

where N represents nitrogen, Z can be oxygen or sulfur and R⁴ can behydrogen, a halogen, a hydrocarbyl group, or a substituted hydrocarbylgroup. Generally R⁴ can be any of the halogens, hydrocarbyl groups, orsubstituted hydrocarbyl groups described herein (e.g., in thedescription of groups suitable for use as R² and/or R³).

In an embodiment, the CATCOMP comprises a metal salt complex,alternatively a metal-salt complex of an imine bis(phenolate) compound,alternatively a metal salt complex of an imine bis(phenolate) compoundwhich can have Structure V.

In Structure V, O and N represent oxygen and nitrogen respectively Qrepresents a donor group which can have Structure (VI), (VII) or (VIII).

and M is a Group 3 to Group 12 transition metal or lanthanide. Referringto Structure V, X⁰ can be a neutral ligand and have a value of 0, 1, or2; X¹ can be a monoanionic ligand, and b have a value of 0, 1, 2, 3, or4; and X² can be a dianionic ligand, and c have a value of 0 or 1.

In an embodiment, R, R², R³, R⁴, and Q of Structure V corresponds to R,R², R³, R⁴, and Q of Structure I respectively such that the groups,features and aspects utilized to describe R², R³, R⁴, and Q of StructureI may be used to describe the corresponding R, R², R³, R⁴, and Q ofStructure V. One or more of R, R², R³, and R⁴ may each be the same ordifferent.

Generally the metal atom of the metal salt complex of the iminebis(phenol) compound (e.g., M in Structure V) can be any metal atom. Inan aspect, the metal atom of the metal salt can be a transition metal ora lanthanide. In an embodiment, suitable metal salts can comprise, orconsist essentially of, a Group 3-12 transition metal; alternatively, aGroup 4-10 transition metal; alternatively, a Group 6-9 transitionmetal; alternatively, a Group 7-8 transition metal; alternatively, aGroup 4 transition metal; alternatively, a Group 5 transition metalalternatively, a Group 6 transition metal; alternatively, a Group 7transition metal; alternatively, a Group 8 transition metal;alternatively, a Group 9 transition metal; or alternatively, a Group 10transition metal. In some embodiments, the metal salt can comprisetitanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium,molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium,platinum, copper, or zinc. Alternatively M is a Group 4 transitionmetal. Alternatively, M is titanium. Alternatively, M is zirconium.Alternatively, M is hafnium.

Generally, the metal atom of the metal can have any positive oxidationstate available to the metal atom. In an embodiment, the oxidation stateof M is equal to (b+2c+2). In an embodiment, the transition metal canhave an oxidation state of from +2 to +6; alternatively, from +2 to +4;or alternatively, from +2 to +3. In some embodiments, the metal atom ofthe transition metal salt, ML_(n) can have an oxidation state of +1;alternatively, +2; alternatively, +3; or alternatively, +4. For example,the most common oxidation state for Ti, Zr, and Hf can be +4; therefore,c can be equal to zero and b can be equal to 2 (two monoanionicligands), or b can be equal to zero and c can be equal to 1 (onedianionic ligand). The most common oxidation state for V and Ta can be+5; therefore, for instance, b can be equal to one (one monoanionicligand) and c can be equal to 1 (one dianionic ligand).

Referring to Structure V, X⁰ can be a neutral ligand, and the integer ain Structure V can be 0, 1 or 2. In an aspect, suitable neutral ligandscan include sigma-donor solvents that contain an atom (or atoms) thatcan coordinate to the metal atom in Structure V. Examples of suitablecoordinating atoms include, but are not limited to, O, N, S, and P, orcombinations of these atoms. The neutral ligand can be unsubstituted orcan be substituted. Substituent groups are independently describedherein and can be utilized, without limitation to further describe aneutral ligand which can be utilized as X⁰ in Structure V. In someaspects, the neutral ligand can be a Lewis base. When the integer a isequal to 2, it is contemplated that the two neutral ligands can be thesame or different and the descriptions set forth herein apply to eachligand independently.

In an aspect, X⁰, can be an ether, a thioether, an amine, a nitrile, ora phosphine. In another aspect, X⁰, can be an acyclic ether, a cyclicether, an acyclic thioether, a cyclic thioether, a nitrile, an acyclicamine, a cyclic amine, an acyclic phosphine, a cyclic phosphine, orcombinations thereof. In other aspects, X⁰, can be an acyclic ether or acyclic ether; alternatively, an acyclic thioether or a cyclic thioether;alternatively, an acyclic amine or a cyclic amine; alternatively, anacyclic phosphine or a cyclic phosphine; alternatively, an acyclicether; alternatively, a cyclic ether; alternatively, an acyclicthioether; alternatively, a cyclic thioether; alternatively, a nitrile;alternatively, an acyclic amine; alternatively, a cyclic amine;alternatively, an acyclic phosphine; or alternatively, a cyclicphosphine. Further, X⁰ can include any substituted analogs of anyacyclic ether, cyclic ether, acyclic thioether, cyclic thioether,nitrile, acyclic amine, cyclic amine, acyclic phosphine, or cyclicphosphine, as disclosed herein.

In an aspect, X⁰ can be a nitrile having the formula R^(1q)C≡N, an etherhaving the formula R^(2q)—O—R^(3q), a thioether having the formulaR^(4q)—S—R^(5q), an amine having the formula NR^(6q)R^(7q)R^(8q),NHR^(6q)R^(7q), or NH₂R^(6q), or a phosphine having the formulaPR^(9q)R^(10q)R^(11q), PHR^(9q)R^(10q), or PH₂R^(9q); alternatively, anitrile having the formula R^(1q)C≡N, an ether having the formulaR^(2q)—O—R^(3q), a thioether having the formula R^(4q)—S—R^(5q), anamine having the formula NR^(6q)R^(7q)R^(8q), or a phosphine having theformula PR^(9q)R^(10q)R^(11q); or alternatively, a nitrile having theformula R^(1q)C≡N, an ether having the formula R^(2q)—O—R^(3q), athioether having the formula R^(4q)—S—R^(5q), an amine having theformula NR^(6q)R^(7q)R^(8q), or a phosphine having the formulaPR^(9q)R^(10q)R^(11q). In an aspect, X⁰ can be a nitrile having theformula R^(1q)C≡N; alternatively, an ether having the formulaR^(2q)—O—R^(3q); alternatively, a thioether having the formulaR^(4a)—S—R^(5a); alternatively, an amine having the formulaNR^(6q)R^(7q)R^(8q), NHR^(6q)R^(7q), or NH₂R^(6q); alternatively, aphosphine having the formula PR^(9q)R^(10q)R^(11q), PHR^(9q)R^(10q), orPH₂R^(9q); or alternatively, a phosphine having the formulaPR^(9q)R^(10q)R^(11q).

In an aspect, R^(1q) of the nitrile having the formula R^(1q)C≡N, R^(2q)and R^(3q) of the ether having formula R^(2q)—O—R^(3q), R^(4q) andR^(5q) of the thioether having the formula R^(4q)—S—R^(5q), R^(6q),R^(7q), and R^(8q) of the amine having the formula NR^(6q)R^(7q)R^(8q),NHR^(6q)R^(7q), or NH₂R^(6q), and R^(9q), R^(10q), and R^(11q) of thephosphine having the formula PR^(9q)R^(10q)R^(11q), PHR^(9q)R^(10q), orPH₂R^(9q), independently can be a C₁ to C₁₈ hydrocarbyl group;alternatively, a C₁ to C₁₅ hydrocarbyl group; alternatively, a C₁ to C₁₂hydrocarbyl group; alternatively, a C₁ to C₈ hydrocarbyl group; oralternatively, a C₁ to C₆ hydrocarbyl group. It should also be notedthat R^(2q) and R^(3q) of the ether having formula R^(2q)—O—R^(3q),R^(4q) and R^(5q) of the thioether having the formula R^(4q)—S—R^(5q),any two of R^(6q), R^(7q), and R^(8q) of the amine having the formulaNR^(6q)R^(7q)R^(8q) or NHR^(6q)R^(7q), and/or any two of R^(9q),R^(10q), and R^(11q) of the phosphine having the formulaPR^(9q)R^(10q)R^(11q) or PHR^(9q)R^(10q) can be joined to form a ringcontaining the ether oxygen atom, the thioether sulfur atom, the aminenitrogen atom, or the phosphine phosphorus atom to form a cyclic ether,thioether, amine, or phosphine, respectively, as described herein inregards to cyclic ethers, thioethers, amines, and phosphines.

In an aspect, R^(1q) of the nitrile having the formula R^(1q)C≡N, R^(2q)and R^(3q) of the ether having formula R^(2q)—O—R^(3q), R^(4q) andR^(5q) of the thioether having the formula R^(4q)—S—R^(5q), R^(6q),R^(7q), and R^(8q) of the amine having the formula NR^(6q)R^(7q)R^(8q),NHR^(6q)R^(7q), or NH₂R^(6q), and R^(9q)R^(10q), and R^(11q) of thephosphine having the formula PR^(9q)R^(10q)R^(1lq), PHR^(9q)R^(10q), orPH₂R^(9q), independently be any hydrocarbyl group disclosed herein. Thehydrocarbyl group can be, for instance, any alkyl group, cycloalkylgroup, aryl group, or aralkyl group disclosed herein.

In another aspect X⁰, in Structure V independently can be a C₂-C₃₀ether, a C₂-C₃₀ thioether, a C₂-C₂₀ nitrile, a C₁-C₃₀ amine, or a C₁-C₃₀phosphine; alternatively, a C₂-C₁₈ ether; alternatively, a C₂-C₁₈thioether; alternatively, a C₂-C₁₂ nitrile; alternatively, a C₁-C₁₈amine; or alternatively, a C₁-C₁₈ phosphine. In some aspects, eachneutral ligand independently can be a C₂-C₁₂ ether, a C₂-C₁₂ thioether,a C₂-C₈ nitrile, a C₁-C₁₂ amine, or a C₁-C₁₂ phosphine; alternatively, aC₂-C₁₀ ether; alternatively, a C₂-C₁₀ thioether; alternatively, a C₂-C₆nitrile; alternatively, a C₁-C₈ amine; or alternatively, a C₁-C₈phosphine.

Suitable ethers which can be utilized as X⁰, either alone or incombination, can include, but are not limited to, dimethyl ether,diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methylpropyl ether, methyl butyl ether, diphenyl ether, ditolyl ether,tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran,2,3-dihydrofuran, 2,5-dihydrofuran, furan, benzofuran, isobenzofuran,dibenzofuran, tetrahydropyran, 3,4-dihydro-2H-pyran,3,6-dihydro-2H-pyran, 2H-pyran, 4H-pyran, 1,3-dioxane, 1,4-dioxane,morpholine, and the like, including substituted derivatives thereof.

Suitable thioethers which can be utilized as X⁰, either alone or incombination, can include, but are not limited to, dimethyl thioether,diethyl thioether, dipropyl thioether, dibutyl thioether, methyl ethylthioether, methyl propyl thioether, methyl butyl thioether, diphenylthioether, ditolyl thioether, thiophene, benzothiophene,tetrahydrothiophene, thiane, and the like, including substitutedderivatives thereof.

Suitable nitriles which can be utilized as X⁰, either alone or incombination, can include, but are not limited to, acetonitrile,propionitrile, butyronitrile, benzonitrile, 4-methylbenzonitrile, andthe like, including substituted derivatives thereof.

Suitable amines which can be utilized as X⁰, either alone or incombination, can include, but are not limited to, methyl amine, ethylamine, propyl amine, butyl amine, dimethyl amine, diethyl amine,dipropyl amine, dibutyl amine, trimethyl amine, triethyl amine,tripropyl amine, tributyl amine, aniline, diphenylamine, triphenylamine,tolylamine, xylylamine, ditolylamine, pyridine, quinoline, pyrrole,indole, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine,2,5-dimethylpyrrole, 2,5-diethylpyrrole, 2,5-dipropylpyrrole,2,5-dibutylpyrrole, 2,4-dimethylpyrrole, 2,4-diethylpyrrole,2,4-dipropylpyrrole, 2,4-dibutylpyrrole, 3,4-dimethylpyrrole,3,4-diethylpyrrole, 3,4-dipropylpyrrole, 3,4-dibutylpyrrole,2-methylpyrrole, 2-ethylpyrrole, 2-propylpyrrole, 2-butylpyrrole,3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole,3-ethyl-2,4-dimethylpyrrole, 2,3,4,5-tetramethylpyrrole,2,3,4,5-tetraethylpyrrole, and the like, including substitutedderivatives thereof. Suitable amines can be primary amines, secondaryamines, or tertiary amines.

Suitable phosphines which can be utilized as X⁰, either alone or incombination, can include, but are not limited to, trimethylphosphine,triethylphosphine, tripropylphosphine, tributylphosphine,phenylphosphine, tolylphosphine, diphenylphosphine, ditolylphosphine,triphenylphosphine, tritolylphosphine, methyldiphenylphosphine,dimethylphenylphosphine, ethyldiphenylphosphine, diethylphenylphosphine,and the like, including substituted derivatives thereof.

In an aspect, X⁰ can be azetidine, oxetane, thietane, dioxetane,dithietane, tetrahydropyrrole, dihydropyrrole, pyrrole, indole,isoindole, tetrahydrofuran, 2-methyltetrahydrofuran,2,5-dimethyltetrahydrofuran, dihydrofuran, furan, benzofuran,isobenzofuran, tetrahydrothiophene, dihydrothiophene, thiophene,benzothiophene, isobenzothiophene, imidazolidine, pyrazole, imidazole,oxazolidine, oxazole, isoxazole, thiazolidine, thiazole, isothiazole,benzothiazole, dioxolane, dithiolane, triazole, dithiazole, piperidine,pyridine, dimethyl amine, diethyl amine, tetrahydropyran, dihydropyran,pyran, thiane, piperazine, diazine, oxazine, thiazine, dithiane,dioxane, dioxin, triazine, triazinane, trioxane, oxepin, azepine,thiepin, diazepine, morpholine, quinoline, tetrahydroquinone,bicyclo[3.3.1]tetrasiloxane, or acetonitrile; alternatively, azetidine,oxetane, thietane, dioxetane, dithietane, tetrahydropyrrole,tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran,tetrahydrothiophene, imidazolidine, oxazolidine, oxazole, thiazolidine,thiazole, dioxolane, dithiolane, piperidine, tetrahydropyran, pyran,thiane, piperazine, oxazine, thiazine, dithiane, dioxane, dioxin,triazinane, trioxane, azepine, thiepin, diazepine, morpholine,1,2-thiazole, or bicyclo[3.3.1]tetrasiloxane; alternatively,tetrahydropyrrole, tetrahydrofuran, 2-methyltetrahydrofuran,2,5-dimethyltetrahydrofuran, tetrahydrothiophene, oxazolidine,thiazolidine, dioxolane, dithiolane, dithiazole, piperidine,tetrahydropyran, pyran, thiane, piperazine, dithiane, dioxane, dioxin,trioxane, or morpholine; alternatively, tetrahydrofuran,2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran,tetrahydrothiophene, dioxolane, dithiolane, tetrahydropyran, pyran,thiane, dithiane, dioxane, dioxin, or trioxane; alternatively,tetrahydrofuran, dioxolane, tetrahydropyran, dioxane, or trioxane;alternatively, pyrrole, furan, pyrazole, imidazole, oxazole, isoxazole,thiazole, isothiazole, triazole, pyridine, dimethyl amine, diethylamine, diazine, triazine, or quinoline; alternatively, pyrrole, furan,imidazole, oxazole, thiazole, triazole, pyridine, dimethyl amine,diethyl amine, diazine, or triazine; or alternatively, furan, oxazole,thiazole, triazole, pyridine, diazine, or triazine. In some aspects, X⁰can be azetidine; alternatively, oxetane; alternatively, thietane;alternatively, dioxetane; alternatively, dithietane; alternatively,tetrahydropyrrole; alternatively, dihydropyrrole, alternatively,pyrrole; alternatively, indole; alternatively, isoindole; alternatively,tetrahydrofuran; alternatively, 2-methyltetrahydrofuran; alternatively,2,5-dimethyltetrahydrofuran; alternatively, dihydropyrrole;alternatively, furan; alternatively, benzofuran; alternatively,isobenzofuran; alternatively, tetrahydrothiophene; alternatively,dihydrothiophene; alternatively, thiophene; alternatively,benzothiophene; alternatively, isobenzothiophene; alternatively,imidazolidine; alternatively, pyrazole; alternatively, imidazole;alternatively, oxazolidine; alternatively, oxazole; alternatively,isoxazole; alternatively, thiazolidine; alternatively, thiazole;alternatively, benzothiazole; alternatively, isothiazole; alternatively,dioxolane; alternatively, dithiolane; alternatively, triazole;alternatively, dithiazole; alternatively, piperidine; alternatively,pyridine; alternatively, dimethyl amine; alternatively, diethyl amine;alternatively, tetrahydropyran; alternatively, dihydropyran;alternatively, pyran; alternatively, thiane; alternatively, piperazine;alternatively, diazine; alternatively, oxazine; alternatively, thiazine;alternatively, dithiane; alternatively, dioxane; alternatively, dioxin;alternatively, triazine; alternatively, triazinane; alternatively,trioxane; alternatively, oxepin; alternatively, azepine; alternatively,thiepin; alternatively, diazepine; alternatively, morpholine;alternatively, quinoline; alternatively, tetrahydroquinone;alternatively, bicyclo[3.3.1]tetrasiloxane; or alternatively,acetonitrile.

In another aspect, X⁰ can be azetidine, tetrahydropyrrole,dihydropyrrole, pyrrole, indole, isoindole, imidazolidine, pyrazole,imidazole, oxazolidine, oxazole, isoxazole, thiazolidine, thiazole,isothiazole, triazole, benzotriazole, dithiazole, piperidine, pyridine,dimethyl amine, diethyl amine, piperazine, diazine, oxazine, thiazine,triazine, azepine, diazepine, morpholine, quinoline, ortetrahydroisoquinoline. In another aspect, X⁰ can be thietane,dithietane, tetrahydrothiophene, dihydrothiophene, thiophene,benzothiophene, isobenzothiophene, thiazolidine, thiazole, isothiazole,dithiolane, dithiazole, thiane, thiazine, dithiane, or thiepin. Inanother aspect, X⁰ can be tetrahydrofuran, furan, methyltetrahydrofuran,dihydrofuran, tetrahydropyran, 2,3-dihydropyran, 1,3-dioxane,1,4-dioxane, morpholine, N-methylmorpholine, acetonitrile,propionitrile, butyronitrile, benzonitrile, pyridine, ammonia, methylamine, ethyl amine, dimethyl amine, diethyl amine, trimethyl amine,triethyl amine, trimethylphosphine, triethylphosphine,triphenylphosphine, tri-n-butylphosphine, methyl isocyanide, n-butylisocyanide, phenyl isocyanide, SMe₂, thiophene, or tetrahydrothiophene.In another aspect, X⁰ can be tetrahydrofuran, methyltetrahydrofuran,tetrahydropyran, 1,4-dioxane, acetonitrile, pyridine, dimethyl amine,diethyl amine, ammonia, trimethyl amine, triethyl amine,trimethylphosphine, triethylphosphine, triphenylphosphine, SMe₂, ortetrahydrothiophene; alternatively, tetrahydrofuran,methyltetrahydrofuran, tetrahydropyran, or 1,4-dioxane; alternatively,ammonia, trimethylamine, or triethylamine; or alternatively,trimethylphosphine, triethylphosphine, or triphenylphosphine. Yet, inanother aspect, X⁰ can be tetrahydrofuran, acetonitrile, pyridine,ammonia, dimethyl amine, diethyl amine, trimethyl amine,trimethylphosphine, or triphenylphosphine; alternatively,tetrahydrofuran, acetonitrile, pyridine, dimethyl amine, diethyl amine,trimethyl amine, trimethylphosphine, or triphenylphosphine;alternatively, tetrahydrofuran, acetonitrile, dimethyl amine, diethylamine, or pyridine; alternatively, tetrahydrofuran; alternatively,acetonitrile; alternatively, dimethyl amine; alternatively, diethylamine; or alternatively, pyridine.

X¹ in Structure V can be a monoanionic ligand, and the integer b inStructure V can be 0, 1, 2, 3, or 4. X¹ can be a hydrogen (hydride), ahalide, a C₁ to C₁₈ hydrocarbyl group, a hydrocarbyloxide group, ahydrocarbylamino group, a hydrocarbylsilyl group, or ahydrocarbylaminosilyl group. If b is greater than 1, each X¹ group ofStructure V, can be the same or a different. In an embodiment, b isgreater than 1 and each X¹ can independently be a hydrogen (hydride), ahalide, a C₁ to C₁₈ hydrocarbyl group, a hydrocarbyloxide group, ahydrocarbylamino group, a hydrocarbylsilyl group, or ahydrocarbylaminosilyl group.

In one aspect, X¹ can be hydrogen, a halide (e.g., F, Cl, Br, or I), aC₁ to C₁₈ hydrocarbyl group, a hydrocarbyloxide group, ahydrocarbylamino group, a hydrocarbylsilyl group, or ahydrocarbylaminosilyl group. In another aspect, X¹ can be hydrogen, ahalide, a C₁ to C₁₂ hydrocarbyl group, a hydrocarbyloxide group, ahydrocarbylamino group, a hydrocarbylsilyl group, or ahydrocarbylaminosilyl group. In yet another aspect, X¹ can be hydrogen,a halide, a C₁ to C₁₀ hydrocarbyl group, a hydrocarbyloxide group, ahydrocarbylamino group, a hydrocarbylsilyl group, or ahydrocarbylaminosilyl group. In still another aspect, X¹ can behydrogen, a halide, a C₁ to C₈ hydrocarbyl group, a hydrocarbyloxidegroup, a hydrocarbylamino group, a hydrocarbylsilyl group, or ahydrocarbylaminosilyl group.

The hydrocarbyl group which can be X¹ in Structure V can be any C₁ toC₁₈ hydrocarbyl group, any C₁ to C₁₂ hydrocarbyl group, any C₁ to C₁₀hydrocarbyl group, or any C₁ to C₈ hydrocarbyl group disclosed herein. Ahydrocarbyloxide group is used generically herein to include, forinstance, alkoxy, aryloxy, and -(alkyl or aryl)-O-(alkyl or aryl)groups, and these groups can comprise up to about 18 carbon atoms (e.g.,C₁ to C₁₈, C₁ to C₁₂, C₁ to C₁₀, or C₁ to C₈ hydrocarbyloxide groups).Illustrative and non-limiting examples of hydrocarbyloxide groups caninclude methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy,acetylacetonate (acac), and the like. The term hydrocarbylamino group isused generically herein to refer collectively to, for instance,alkylamino, arylamino, dialkylamino, diarylamino, and -(alkyl oraryl)-N-(alkyl or aryl) groups, and the like. Unless otherwisespecified, the hydrocarbylamino groups which can be X¹ in Structure Vcan comprise up to about 18 carbon atoms (e.g., C₁ to C₁₈, C₁ to C₁₂, C₁to C₁₀, or C₁ to C₈ hydrocarbylamino groups). The hydrocarbylsilyl groupwhich can be X¹ in Structure V can be any C₁ to C₁₈ hydrocarbylsilylgroup, any C₁ to C₁₂ hydrocarbylsilyl group, any C₁ to C₁₀hydrocarbylsilyl group, or any C₁ to C₈ hydrocarbylsilyl group,disclosed herein. A hydrocarbylaminosilyl group is used herein to referto groups containing at least one hydrocarbon moiety, at least onenitrogen atom, and at least one silicon atom. Illustrative andnon-limiting examples of hydrocarbylaminosilyl groups which can be X¹can include, but are not limited to —N(SiMe₃)₂, —N(SiEt₃)₂, and thelike. Unless otherwise specified, the hydrocarbylaminosilyl groups whichcan be X¹ can comprise up to about 18 carbon atoms (e.g., C₁ to C₁₈, C₁to C₁₂, C₁ to C₁₀, or C₁ to C₈ hydrocarbylaminosilyl groups).

In accordance with an aspect of this disclosure, X¹ in Structure V canbe a halide; alternatively, a C₁ to C₁₈ hydrocarbyl group;alternatively, a C₁ to C₁₈ hydrocarbyloxide group; alternatively, a C₁to C₁₈ hydrocarbylamino group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminosilyl group. In accordance with another aspect, X¹ canbe hydrogen; alternatively, F; alternatively, Cl; alternatively, Br;alternatively, I; alternatively, a C₁ to C₁₈ hydrocarbyl group;alternatively, a C₁ to C₁₈ hydrocarbyloxide group; alternatively, a C₁to C₁₈ hydrocarbylamino group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminosilyl group. In accordance with yet another aspect, orat least one X¹ can be hydrogen, a halide, methyl, phenyl, benzyl, analkoxy, an aryloxy, acetylacetonate, an alkylamino, a dialkylamino, atrihydrocarbylsilyl, or a hydrocarbylaminosilyl; alternatively,hydrogen, a halide, methyl, phenyl, or benzyl; alternatively, an alkoxy,an aryloxy, or acetylacetonate; alternatively, an alkylamino or adialkylamino; alternatively, a trihydrocarbylsilyl orhydrocarbylaminosilyl; alternatively, hydrogen or a halide;alternatively, methyl, phenyl, benzyl, an alkoxy, an aryloxy,acetylacetonate, an alkylamino, or a dialkylamino; alternatively,hydrogen; alternatively, a halide; alternatively, methyl; alternatively,phenyl; alternatively, benzyl; alternatively, an alkoxy; alternatively,an aryloxy; alternatively, acetylacetonate; alternatively, analkylamino; alternatively, a dialkylamino; alternatively, atrihydrocarbylsilyl; or alternatively, a hydrocarbylaminosilyl. In theseand other aspects, the alkoxy, aryloxy, alkylamino, dialkylamino,trihydrocarbylsilyl, and hydrocarbylaminosilyl can be a C₁ to C₁₈, a C₁to C₁₂, a C₁ to C₁₀, or a C₁ to C₈ alkoxy, aryloxy, alkylamino,dialkylamino, trihydrocarbylsilyl, or hydrocarbylaminosilyl.

X² in Structure V can be a dianionic ligand, and the integer c inStructure V can be either 0 or 1. In one aspect, X² can be ═O, ═NR^(2A),or ═CR^(2B)R^(2C). In another aspect, X² can be ═O; alternatively, X²can be ═NR^(2A); or alternatively, X² can be ═CR^(2B)R^(2C).Independently, R^(2A), R^(2B), and R^(2C) can be hydrogen or any C₁ toC₁₈ hydrocarbyl group disclosed herein; alternatively, hydrogen or anyC₁ to C₁₂ hydrocarbyl group disclosed herein; alternatively, hydrogen orany C₁ to C₁₀ hydrocarbyl group disclosed herein; or alternatively,hydrogen or any C₁ to C₈ hydrocarbyl group disclosed herein. As anexample, R^(2A), R^(2B), and R^(2C) can each independently be hydrogenor any C₁ to C₁₂, C₁ to C₈, or any C₁ to C₆ alkyl group disclosedherein.

In an embodiment, an imine bis(phenol) compound has Structure IX:

where the groups utilized to describe R, R², and R³ of Structure I maybe utilized to describe R, R², and R³ respectively of Structure IX.

In an embodiment, an imine bis(phenol) compound has Structure X:

where the groups utilized to describe R, and R² of Structure I may beutilized to describe R and R² respectively of Structure X. In anembodiment of Structure X, R is a t-butyl group and R² is hydrogen.Alternatively R and R² are t-butyl groups, alternatively R is a methylgroup and R² is hydrogen, alternatively R and R² are chloride,alternatively R is adamantyl and R² is methyl, alternatively R ismethoxy and R² is hydrogen, or alternatively R and R² are hydrogen.

In an embodiment, an imine phenol compound has Structure XI:

where the groups utilized to describe R, R², and R³ of Structure I maybe utilized to describe R, R², and R³ respectively of Structure XI.

In an embodiment, an imine phenol compound has Structure XII:

where the groups utilized to describe R and R² of Structure I may beutilized to describe R and R² respectively of Structure XII. In anembodiment of Structure XII, R and R² are methyl groups, oralternatively R is methoxy and R² is hydrogen.

In an embodiment, a metal salt complex prepared from an iminebis(phenol) compound (and suitable for use in a CATCOMP of the presentdisclosure) has Structure XIII:

where M is titanium, zirconium, or hafnium and R, R², R³, X⁰, and X¹ areof the type described herein and X⁰ is optional. In an embodiment ofStructure XIII, M is zirconium and R is a t-butyl group. Alternatively,M is hafnium and R is a t-butyl group; alternatively, M is zirconium andR and R² are t-butyl groups, alternatively M is zirconium and R is amethyl group, alternatively M is zirconium and R and R² are chloride, oralternatively M is zirconium, R is adamantyl and R² is methyl.

In an embodiment, a metal salt complex prepared from an iminebis(phenol) compound (and suitable for use in a CATCOMP of the presentdisclosure) has Structure XIV:

where the groups utilized to describe R and R² of Structure I may beutilized to describe R and R² respectively of Structure XIV and Et₂O isoptional.

In an embodiment, a metal salt complex prepared from an iminebis(phenol) compound (and suitable for use in a CATCOMP of the presentdisclosure) has Structure XV where Et₂O is optional:

In an embodiment, a metal salt complex prepared from an iminebis(phenol) compound (and suitable for use in a CATCOMP of the presentdisclosure) has any of Structures XVI, XVII, XVIII, XIX, XX, or XXI:

In an embodiment, the metallocene-containing compound in the CATCOMP isan unbridged metallocene, designated MTE-A, which, when utilized as anethylene polymerization catalyst. Herein, the term “metallocene”describes a compound comprising at least one η³ toη⁵-cycloalkadienyl-type moiety, wherein η³ to η⁵-cycloalkadienylmoieties include cyclopentadienyl ligands, indenyl ligands, fluorenylligands, and the like, including partially saturated or substitutedderivatives or analogs of any of these. Possible substituents on theseligands include hydrogen, therefore the description “substitutedderivatives thereof” in this disclosure comprises partially saturatedligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, substituted partially saturated indenyl, substitutedpartially saturated fluorenyl, and the like.

In an embodiment, MTE-A is a compound that may be characterized by oneof general formulas 1 or 2:

where each X is independently F, Cl, Br, I, methyl, benzyl, phenyl, H,BH₄, a hydrocarbyloxide group having up to 20 carbon atoms, ahydrocarbylamino group having up to 20 carbon atoms, atrihydrocarbylsilyl group having up to 20 carbon atoms, OBR′₂ wherein R′may be an alkyl group having up to 12 carbon atoms or an aryl grouphaving up to 12 carbon atoms, and SO₃R″, wherein R″ may be an alkylgroup having up to 12 carbon atoms or an aryl group having up to 12carbon atoms; Y is a CR₂ or SiR₂ group where R is hydrogen or ahydrocarbyl group; Cp^(A), Cp^(B), Cp^(C), and Cp^(D) are eachindependently a substituted or unsubstituted cyclopentadienyl group,indenyl group, or flourenyl group and where any substituent on Cp^(A),Cp^(B), Cp^(C), and Cp^(D) can be H, a hydrocarbyl group having up to 18carbon atoms or a hydrocarbylsilyl group having up to 18 carbon atoms.

In an embodiment, MTE-A is a dinuclear compound wherein each metalmoiety has the same structural characteristic described previouslyherein. In an embodiment, MTE-A is a nonbridged metallocene. Nonlimitingexamples of compounds suitable for use in this disclosure as MTE-A arerepresented by structures (1)-(13):

Other nonlimiting examples of metallocene compounds that may be suitablyemployed as MTE-A in a CATCOMP of the type disclosed herein includebis(cyclopentadienyl)hafnium dichloride;bis(n-butylcyclopentadienyl)bis(di-t-butylamido)hafnium;bis(n-propylcyclopentadienyl)zirconium dichloride;bis(pentamethylcyclopentadienyl)zirconium dichloride;bis(1-propylindenyl)zirconium dichloride; or any combination thereof.

In an alternative embodiment, the CATCOMP comprises a bridgedmetallocene compound hereinafter designated MTE-B. In an embodiment,MTE-B can be characterized by one of general formulas 3 or 4:

where M is Ti, Zr or Hf; each X is independently F, Cl, Br, I, methyl,phenyl, benzyl, H, BH₄, a hydrocarbyloxide group having up to 20 carbonatoms, a hydrocarbylamino group having up to 20 carbon atoms, atrihydrocarbylsilyl group having up to 20 carbon atoms, OBR′₂ wherein R′may be an alkyl group having up to 12 carbon atoms or an aryl grouphaving up to 12 carbon atoms, or SO₃R″ wherein R″ may be an alkyl grouphaving up to 12 carbon atoms or an aryl group having up to 12 carbonatoms; Y is a CR₂, SiR₂, or R₂CCR₂ group which may be linear or cyclicand where R is hydrogen or a hydrocarbyl group; Cp^(A), Cp^(B), Cp^(C),and Cp^(D) are each independently a substituted or unsubstitutedcyclopentadienyl group, indenyl group, or flourenyl group and where anysubstituent on Cp^(A), Cp^(B), Cp^(C), and Cp^(D) can be H, ahydrocarbyl group having up to 18 carbon atoms or a hydrocarbylsilylgroup having up to 18 carbon atoms. E represents a bridging group whichmay comprise (i) a cyclic or heterocyclic moiety having up to 18 carbonatoms, (ii) a group represented by the general formulaE^(A)R^(3A)R^(4A), wherein E^(A) is C, Si, Ge, or B, and R^(3A) andR^(4A) are independently H or a hydrocarbyl group having up to 18 carbonatoms, (iii) a group represented by the general formula—CR^(3B)R^(4B)—CR^(3C)R^(4C)—, wherein R^(3B), R^(4B), R^(3C), andR^(4C) are independently H or a hydrocarbyl group having up to 10 carbonatoms, or (iv) a group represented by the general formula SiR₂—CR₂ whereX is Si or C and R is a hydrogen or hydrocarbyl group; or—SiR^(3D)R^(4D)—SiR^(3E)R^(4E)—, wherein R^(3D), R^(4D), R^(3E), andR^(4E) are independently H or a hydrocarbyl group having up to 10 carbonatoms, and wherein at least one of R^(3A), R^(3B), R^(4A), R^(4B),R^(3C), R^(4C), R^(3D), R^(4D), R^(3E), R^(4E), or the substituent onCp, Cp₁, or Cp₂, is (1) a terminal alkenyl group having up to 12 carbonatoms or (2) a dinuclear compound wherein each metal moiety has the samestructural characteristic as MTE-B. Nonlimiting examples of compoundssuitable for use in this disclosure as MTE-B are represented bystructures (14)-(29):

In an embodiment, the CATCOMP further comprises a chemically-treatedsolid oxide which may function as an activator-support. Alternatively,the chemically-treated solid oxide can comprise a clay mineral, apillared clay, an exfoliated clay, an exfoliated clay gelled intoanother oxide matrix, a layered silicate mineral, a non-layered silicatemineral, a layered aluminosilicate mineral, a non-layeredaluminosilicate mineral, or any combination thereof.

Generally, chemically-treated solid oxides exhibit enhanced acidity ascompared to the corresponding untreated solid oxide compound. Thechemically-treated solid oxide also functions as a catalyst activator ascompared to the corresponding untreated solid oxide. While thechemically-treated solid oxide activates the transition-metal saltcomplex in the absence of co-catalysts, co-catalysts may also beincluded in the catalyst composition. The activation function of theactivator-support is evident in the enhanced activity of catalystcomposition as a whole, as compared to a catalyst composition containingthe corresponding untreated solid oxide. However, it is believed thatthe chemically-treated solid oxide can function as an activator, even inthe absence of an organoaluminum compound, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.

The chemically-treated solid oxide can comprise a solid oxide treatedwith an electron-withdrawing anion. While not intending to be bound bythe following statement, it is believed that treatment of the solidoxide with an electron-withdrawing component augments or enhances theacidity of the oxide. Thus, either the activator-support exhibits Lewisor Brønsted acidity that is typically greater than the Lewis or Brønstedacid strength of the untreated solid oxide, or the activator-support hasa greater number of acid sites than the untreated solid oxide, or both.One method to quantify the acidity of the chemically-treated anduntreated solid oxide materials is by comparing the polymerizationactivities of the treated and untreated oxides under acid catalyzedreactions.

Chemically-treated solid oxides of this disclosure are formed generallyfrom an inorganic solid oxide that exhibits Lewis acidic or Brønstedacidic behavior and has a relatively high porosity. The solid oxide ischemically-treated with an electron-withdrawing component, typically anelectron-withdrawing anion, to form an activator-support.

According to one aspect of the present disclosure, the solid oxide usedto prepare the chemically-treated solid oxide has a pore volume greaterthan about 0.1 cc/g. According to another aspect of the presentdisclosure, the solid oxide has a pore volume greater than about 0.5cc/g. According to yet another aspect of the present disclosure, thesolid oxide has a pore volume greater than about 1.0 cc/g.

In another aspect, the solid oxide has a surface area of from about 100m²/g to about 1000 m²/g. In yet another aspect, the solid oxide has asurface area of from about 200 m²/g to about 800 m²/g. In still anotheraspect of the present disclosure, the solid oxide has a surface area offrom about 250 m²/g to about 600 m²/g.

The chemically-treated solid oxide can comprise a solid inorganic oxidecomprising oxygen and one or more elements selected from Group 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or of the periodic table, orcomprising oxygen and one or more elements selected from the lanthanideor actinide elements (See: Hawley's Condensed Chemical Dictionary, 11thEd., John Wiley & Sons, 1995; Cotton, F. A., Wilkinson, G., Murillo, C.A., and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed.,Wiley-Interscience, 1999). For example, the inorganic oxide can compriseoxygen and an element, or elements, selected from Al, B, Be, Bi, Cd, Co,Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn,and Zr.

Suitable examples of solid oxide materials or compounds that can be usedto form the chemically-treated solid oxide include, but are not limitedto, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, CO₃O₄, Cr₂O₃, CuO, Fe₂O₃, Ga₂O₃,La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂, TiO₂, V₂O₅,WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixed oxides thereof, andcombinations thereof. For example, the solid oxide can comprise silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, mixed oxides thereof, or any combination thereof.

The solid oxide of this disclosure encompasses oxide materials such asalumina, “mixed oxide” compounds thereof such as silica-alumina, andcombinations and mixtures thereof. The mixed oxide compounds such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form a solid oxide compound. Examplesof mixed oxides that can be used in the activator-support of the presentdisclosure include, but are not limited to, silica-alumina,silica-titania, silica-zirconia, zeolites, various clay minerals,alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria,silica-boria, aluminophosphate-silica, titania-zirconia, and the like.The solid oxide of this disclosure also encompasses oxide materials suchas silica-coated alumina, as described in U.S. Pat. No. 7,884,163, thedisclosure of which is incorporated herein by reference in its entirety.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspectof the present disclosure, the electron-withdrawing component is anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Examples of electron-withdrawing anionsinclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, and the like, including mixtures andcombinations thereof. In addition, other ionic or non-ionic compoundsthat serve as sources for these electron-withdrawing anions also can beemployed in the present disclosure. It is contemplated that theelectron-withdrawing anion can be, or can comprise, fluoride, chloride,bromide, phosphate, triflate, bisulfate, or sulfate, and the like, orany combination thereof, in some aspects of this disclosure. In otheraspects, the electron-withdrawing anion can comprise sulfate, bisulfate,fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate,phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, or any combination thereof.

Thus, for example, the activator-support (e.g., chemically-treated solidoxide) used in the catalyst compositions can be, or can comprise,fluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, or combinations thereof. In one aspect, theactivator-support can be, or can comprise, fluorided alumina, sulfatedalumina, fluorided silica-alumina, sulfated silica-alumina, fluoridedsilica-coated alumina, sulfated silica-coated alumina, phosphatedsilica-coated alumina, and the like, or any combination thereof. Inanother aspect, the activator-support comprises fluorided alumina;alternatively, comprises chlorided alumina; alternatively, comprisessulfated alumina; alternatively, comprises fluorided silica-alumina;alternatively, comprises sulfated silica-alumina; alternatively,comprises fluorided silica-zirconia; alternatively, comprises chloridedsilica-zirconia; or alternatively, comprises fluorided silica-coatedalumina.

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt can beselected from any cation that allows the salt to revert or decomposeback to the acid during calcining. Factors that dictate the suitabilityof the particular salt to serve as a source for the electron-withdrawinganion include, but are not limited to, the solubility of the salt in thedesired solvent, the lack of adverse reactivity of the cation,ion-pairing effects between the cation and anion, hygroscopic propertiesimparted to the salt by the cation, and the like, and thermal stabilityof the anion. Examples of suitable cations in the salt of theelectron-withdrawing anion include, but are not limited to, ammonium,trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H⁺,[H(OEt₂)₂]⁺, and the like.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron-withdrawing components can be contacted with the oxide materialsimultaneously or individually, and in any order that affords thedesired chemically-treated solid oxide acidity. For example, one aspectof this disclosure is employing two or more electron-withdrawing anionsource compounds in two or more separate contacting steps.

Thus, one example of such a process by which a chemically-treated solidoxide is prepared is as follows: a selected solid oxide, or combinationof solid oxides, is contacted with a first electron-withdrawing anionsource compound to form a first mixture; this first mixture is calcinedand then contacted with a second electron-withdrawing anion sourcecompound to form a second mixture; the second mixture is then calcinedto form a treated solid oxide. In such a process, the first and secondelectron-withdrawing anion source compounds can be either the same ordifferent compounds.

According to another aspect of the present disclosure, thechemically-treated solid oxide comprises a solid inorganic oxidematerial, a mixed oxide material, or a combination of inorganic oxidematerials, that is chemically-treated with an electron-withdrawingcomponent, and optionally treated with a metal source, including metalsalts, metal ions, or other metal-containing compounds. Nonlimitingexamples of the metal or metal ion include zinc, nickel, vanadium,titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium,and the like, or combinations thereof. Examples of chemically-treatedsolid oxides that contain a metal or metal ion include, but are notlimited to, chlorided zinc-impregnated alumina, fluoridedtitanium-impregnated alumina, fluorided zinc-impregnated alumina,chlorided zinc-impregnated silica-alumina, fluorided zinc-impregnatedsilica-alumina, sulfated zinc-impregnated alumina, chlorided zincaluminate, fluorided zinc aluminate, sulfated zinc aluminate,silica-coated alumina treated with hexafluorotitanic acid, silica-coatedalumina treated with zinc and then fluorided, and the like, or anycombination thereof.

Any method of impregnating the solid oxide material with a metal can beused. The method by which the oxide is contacted with a metal source,typically a salt or metal-containing compound, can include, but is notlimited to, gelling, co-gelling, impregnation of one compound ontoanother, and the like. If desired, the metal-containing compound isadded to or impregnated into the solid oxide in solution form, andsubsequently converted into the supported metal upon calcining.Accordingly, the solid inorganic oxide can further comprise a metalselected from zinc, titanium, nickel, vanadium, silver, copper, gallium,tin, tungsten, molybdenum, and the like, or combinations of thesemetals. For example, zinc is often used to impregnate the solid oxidebecause it can provide improved catalyst activity at a low cost.

The solid oxide can be treated with metal salts or metal-containingcompounds before, after, or at the same time that the solid oxide istreated with the electron-withdrawing anion. Following any contactingmethod, the contacted mixture of solid compound, electron-withdrawinganion, and the metal ion is typically calcined. Alternatively, a solidoxide material, an electron-withdrawing anion source, and the metal saltor metal-containing compound are contacted and calcined simultaneously.

Various processes are used to form the chemically-treated solid oxideuseful in the present disclosure. The chemically-treated solid oxide cancomprise the contact product of one or more solid oxides with one ormore electron-withdrawing anion sources. It is not required that thesolid oxide be calcined prior to contacting the electron-withdrawinganion source. The contact product typically is calcined either during orafter the solid oxide is contacted with the electron-withdrawing anionsource. The solid oxide can be calcined or uncalcined. Various processesto prepare solid oxide activator-supports that can be employed in thisdisclosure have been reported. For example, such methods are describedin U.S. Pat. Nos. 6,107,230; 6,165,929; 6,294,494; 6,300,271; 6,316,553;6,355,594; 6,376,415; 6,388,017; 6,391,816; 6,395,666; 6,524,987;6,548,441; 6,548,442; 6,576,583; 6,613,712; 6,632,894; 6,667,274; and6,750,302; the disclosures of which are incorporated herein by referencein their entirety.

According to one aspect of the present disclosure, the solid oxidematerial is chemically-treated by contacting it with anelectron-withdrawing component, typically an electron-withdrawing anionsource. Further, the solid oxide material optionally is chemicallytreated with a metal ion, and then calcined to form a metal-containingor metal-impregnated chemically-treated solid oxide. According toanother aspect of the present disclosure, the solid oxide material andelectron-withdrawing anion source are contacted and calcinedsimultaneously.

The method by which the oxide is contacted with the electron-withdrawingcomponent, typically a salt or an acid of an electron-withdrawing anion,can include, but is not limited to, gelling, co-gelling, impregnation ofone compound onto another, and the like. Thus, following any contactingmethod, the contacted mixture of the solid oxide, electron-withdrawinganion, and optional metal ion, is calcined.

The solid oxide activator-support (i.e., chemically-treated solid oxide)thus can be produced by a process comprising:

1) contacting a solid oxide (or solid oxides) with anelectron-withdrawing anion source compound (or compounds) to form afirst mixture; and

2) calcining the first mixture to form the solid oxideactivator-support.

According to another aspect of the present disclosure, the solid oxideactivator-support (chemically-treated solid oxide) is produced by aprocess comprising:

1) contacting a solid oxide (or solid oxides) with a firstelectron-withdrawing anion source compound to form a first mixture;

2) calcining the first mixture to produce a calcined first mixture;

3) contacting the calcined first mixture with a secondelectron-withdrawing anion source compound to form a second mixture; and

4) calcining the second mixture to form the solid oxideactivator-support.

According to yet another aspect of the present disclosure, thechemically-treated solid oxide is produced or formed by contacting thesolid oxide with the electron-withdrawing anion source compound, wherethe solid oxide compound is calcined before, during, or after contactingthe electron-withdrawing anion source, and where there is a substantialabsence of aluminoxanes, organoboron or organoborate compounds, andionizing ionic compounds.

Calcining of the treated solid oxide generally is conducted in anambient atmosphere, typically in a dry ambient atmosphere, at atemperature from about 200° C. to about 900° C., and for a time of about1 minute to about 100 hours. Calcining can be conducted at a temperatureof from about 300° C. to about 800° C., or alternatively, at atemperature of from about 400° C. to about 700° C. Calcining can beconducted for about 30 minutes to about 50 hours, or for about 1 hour toabout 15 hours. Thus, for example, calcining can be carried out forabout 1 to about 10 hours at a temperature of from about 350° C. toabout 550° C. Any suitable ambient atmosphere can be employed duringcalcining. Generally, calcining is conducted in an oxidizing atmosphere,such as air. Alternatively, an inert atmosphere, such as nitrogen orargon, or a reducing atmosphere, such as hydrogen or carbon monoxide,can be used.

According to one aspect of the present disclosure, the solid oxidematerial is treated with a source of halide ion, sulfate ion, or acombination of anions, optionally treated with a metal ion, and thencalcined to provide the chemically-treated solid oxide in the form of aparticulate solid. For example, the solid oxide material can be treatedwith a source of sulfate (termed a “sulfating agent”), a source ofchloride ion (termed a “chloriding agent”), a source of fluoride ion(termed a “fluoriding agent”), or a combination thereof, and calcined toprovide the solid oxide activator. Useful acidic activator-supportsinclude, but are not limited to, bromided alumina, chlorided alumina,fluorided alumina, sulfated alumina, bromided silica-alumina, chloridedsilica-alumina, fluorided silica-alumina, sulfated silica-alumina,bromided silica-zirconia, chlorided silica-zirconia, fluoridedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,alumina treated with hexafluorotitanic acid, silica-coated aluminatreated with hexafluorotitanic acid, silica-alumina treated withhexafluorozirconic acid, silica-alumina treated with trifluoroaceticacid, fluorided boria-alumina, silica treated with tetrafluoroboricacid, alumina treated with tetrafluoroboric acid, alumina treated withhexafluorophosphoric acid, a pillared clay, such as a pillaredmontmorillonite, optionally treated with fluoride, chloride, or sulfate;phosphated alumina or other aluminophosphates optionally treated withsulfate, fluoride, or chloride; or any combination of the above.Further, any of these activator-supports optionally can be treated witha metal ion.

The chemically-treated solid oxide can comprise a fluorided solid oxidein the form of a particulate solid. The fluorided solid oxide can beformed by contacting a solid oxide with a fluoriding agent. The fluorideion can be added to the oxide by forming a slurry of the oxide in asuitable solvent such as alcohol or water including, but not limited to,the one to three carbon alcohols because of their volatility and lowsurface tension. Examples of suitable fluoriding agents include, but arenot limited to, hydrofluoric acid (HF), ammonium fluoride (NH₄F),ammonium bifluoride (NH₄HF₂), ammonium tetrafluoroborate (NH₄BF₄),ammonium silicofluoride (hexafluorosilic ate) ((NH₄)₂SiF₆), ammoniumhexafluorophosphate (NH₄PF₆), hexafluorotitanic acid (H₂TiF₆), ammoniumhexafluorotitanic acid ((NH₄)₂TiF₆), hexafluorozirconic acid (H₂ZrF₆),AlF₃, NH₄AlF₄, analogs thereof, and combinations thereof. Triflic acidand ammonium triflate also can be employed. For example, ammoniumbifluoride (NH₄HF₂) can be used as the fluoriding agent, due to its easeof use and availability.

If desired, the solid oxide is treated with a fluoriding agent duringthe calcining step. Any fluoriding agent capable of thoroughlycontacting the solid oxide during the calcining step can be used. Forexample, in addition to those fluoriding agents described previously,volatile organic fluoriding agents can be used. Examples of volatileorganic fluoriding agents useful in this aspect of the disclosureinclude, but are not limited to, freons, perfluorohexane,perfluorobenzene, fluoromethane, trifluoroethanol, and the like, andcombinations thereof. Calcining temperatures generally must be highenough to decompose the compound and release fluoride. Gaseous hydrogenfluoride (HF) or fluorine (F₂) itself also can be used with the solidoxide if fluorided while calcining Silicon tetrafluoride (SiF₄) andcompounds containing tetrafluoroborate (BF₄ ⁻) also can be employed. Oneconvenient method of contacting the solid oxide with the fluoridingagent is to vaporize a fluoriding agent into a gas stream used tofluidize the solid oxide during calcination.

Similarly, in another aspect of this disclosure, the chemically-treatedsolid oxide comprises a chlorided solid oxide in the form of aparticulate solid. The chlorided solid oxide is formed by contacting asolid oxide with a chloriding agent. The chloride ion can be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Thesolid oxide can be treated with a chloriding agent during the calciningstep. Any chloriding agent capable of serving as a source of chlorideand thoroughly contacting the oxide during the calcining step can beused, such as SiCl₄, SiMe₂Cl₂, TiCl₄, BCl₃, and the like, includingmixtures thereof. Volatile organic chloriding agents can be used.Examples of suitable volatile organic chloriding agents include, but arenot limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, andthe like, or any combination thereof. Gaseous hydrogen chloride orchlorine itself also can be used with the solid oxide during calcining.One convenient method of contacting the oxide with the chloriding agentis to vaporize a chloriding agent into a gas stream used to fluidize thesolid oxide during calcination.

The amount of fluoride or chloride ion present before calcining thesolid oxide generally is from about 1 to about 50% by weight, where theweight percent is based on the weight of the solid oxide, for example,silica-alumina, before calcining. According to another aspect of thisdisclosure, the amount of fluoride or chloride ion present beforecalcining the solid oxide is from about 1 to about 25% by weight, andaccording to another aspect of this disclosure, from about 2 to about20% by weight. According to yet another aspect of this disclosure, theamount of fluoride or chloride ion present before calcining the solidoxide is from about 4 to about 10% by weight. Once impregnated withhalide, the halided oxide can be dried by any suitable method including,but not limited to, suction filtration followed by evaporation, dryingunder vacuum, spray drying, and the like, although it is also possibleto initiate the calcining step immediately without drying theimpregnated solid oxide.

The silica-alumina used to prepare the treated silica-alumina typicallyhas a pore volume greater than about 0.5 cc/g. According to one aspectof the present disclosure, the pore volume is greater than about 0.8cc/g, and according to another aspect of the present disclosure, greaterthan about 1.0 cc/g. Further, the silica-alumina generally has a surfacearea greater than about 100 m²/g. According to another aspect of thisdisclosure, the surface area is greater than about 250 m²/g. Yet, inanother aspect, the surface area is greater than about 350 m²/g.

The silica-alumina utilized in the present disclosure typically has analumina content from about 5 to about 95% by weight. According to oneaspect of this disclosure, the alumina content of the silica-alumina isfrom about 5 to about 50%, or from about 8% to about 30%, alumina byweight. In another aspect, high alumina content silica-alumina compoundscan employed, in which the alumina content of these silica-aluminacompounds typically ranges from about 60% to about 90%, or from about65% to about 80%, alumina by weight. According to yet another aspect ofthis disclosure, the solid oxide component comprises alumina withoutsilica, and according to another aspect of this disclosure, the solidoxide component comprises silica without alumina.

The sulfated solid oxide comprises sulfate and a solid oxide component,such as alumina or silica-alumina, in the form of a particulate solid.Optionally, the sulfated oxide is treated further with a metal ion suchthat the calcined sulfated oxide comprises a metal. According to oneaspect of the present disclosure, the sulfated solid oxide comprisessulfate and alumina. In some instances, the sulfated alumina is formedby a process wherein the alumina is treated with a sulfate source, forexample, sulfuric acid or a sulfate salt such as ammonium sulfate. Thisprocess is generally performed by forming a slurry of the alumina in asuitable solvent, such as alcohol or water, in which the desiredconcentration of the sulfating agent has been added. Suitable organicsolvents include, but are not limited to, the one to three carbonalcohols because of their volatility and low surface tension.

According to one aspect of this disclosure, the amount of sulfate ionpresent before calcining is from about 0.5 to about 100 parts by weightsulfate ion to about 100 parts by weight solid oxide. According toanother aspect of this disclosure, the amount of sulfate ion presentbefore calcining is from about 1 to about 50 parts by weight sulfate ionto about 100 parts by weight solid oxide, and according to still anotheraspect of this disclosure, from about 5 to about 30 parts by weightsulfate ion to about 100 parts by weight solid oxide. These weightratios are based on the weight of the solid oxide before calcining. Onceimpregnated with sulfate, the sulfated oxide can be dried by anysuitable method including, but not limited to, suction filtrationfollowed by evaporation, drying under vacuum, spray drying, and thelike, although it is also possible to initiate the calcining stepimmediately.

According to another aspect of the present disclosure, theactivator-support used in preparing the catalyst compositions of thisdisclosure comprises an ion-exchangeable activator-support, includingbut not limited to silicate and aluminosilicate compounds or minerals,either with layered or non-layered structures, and combinations thereof.In another aspect of this disclosure, ion-exchangeable, layeredaluminosilicates such as pillared clays are used as activator-supports.When the acidic activator-support comprises an ion-exchangeableactivator-support, it can optionally be treated with at least oneelectron-withdrawing anion such as those disclosed herein, thoughtypically the ion-exchangeable activator-support is not treated with anelectron-withdrawing anion.

According to another aspect of the present disclosure, theactivator-support of this disclosure comprises clay minerals havingexchangeable cations and layers capable of expanding. Typical claymineral activator-supports include, but are not limited to,ion-exchangeable, layered aluminosilicates such as pillared clays.Although the term “support” is used, it is not meant to be construed asan inert component of the catalyst composition, but rather is to beconsidered an active part of the catalyst composition, because of itsintimate association with the transition-metal salt complex component.

According to another aspect of the present disclosure, the claymaterials of this disclosure encompass materials either in their naturalstate or that have been treated with various ions by wetting, ionexchange, or pillaring. Typically, the clay material activator-supportof this disclosure comprises clays that have been ion exchanged withlarge cations, including polynuclear, highly charged metal complexcations. However, the clay material activator-supports of thisdisclosure also encompass clays that have been ion exchanged with simplesalts, including, but not limited to, salts of Al(III), Fe(II), Fe(III),and Zn(II) with ligands such as halide, acetate, sulfate, nitrate, ornitrite.

According to another aspect of the present disclosure, theactivator-support comprises a pillared clay. The term “pillared clay” isused to refer to clay materials that have been ion exchanged with large,typically polynuclear, highly charged metal complex cations. Examples ofsuch ions include, but are not limited to, Keggin ions which can havecharges such as 7⁺, various polyoxometallates, and other large ions.Thus, the term pillaring refers to a simple exchange reaction in whichthe exchangeable cations of a clay material are replaced with large,highly charged ions, such as Keggin ions. These polymeric cations arethen immobilized within the interlayers of the clay and when calcinedare converted to metal oxide “pillars,” effectively supporting the claylayers as column-like structures. Thus, once the clay is dried andcalcined to produce the supporting pillars between clay layers, theexpanded lattice structure is maintained and the porosity is enhanced.The resulting pores can vary in shape and size as a function of thepillaring material and the parent clay material used. Examples ofpillaring and pillared clays are found in: T. J. Pinnavaia, Science 220(4595), 365-371 (1983); J. M. Thomas, Intercalation Chemistry, (S.Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press,Inc., (1972); U.S. Pat. Nos. 4,452,910; 5,376,611; and 4,060,480; thedisclosures of which are incorporated herein by reference in theirentirety.

The pillaring process utilizes clay minerals having exchangeable cationsand layers capable of expanding. Any pillared clay that can enhance thepolymerization of olefins in the catalyst composition of the presentdisclosure can be used. Therefore, suitable clay minerals for pillaringinclude, but are not limited to, allophanes; smectites, bothdioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof suchas montmorillonites (bentonites), nontronites, hectorites, or laponites;halloysites; vermiculites; micas; fluoromicas; chlorites; mixed-layerclays; the fibrous clays including but not limited to sepiolites,attapulgites, and palygorskites; a serpentine clay; illite; laponite;saponite; and any combination thereof. In one aspect, the pillared clayactivator-support comprises bentonite or montmorillonite. The principalcomponent of bentonite is montmorillonite.

The pillared clay can be pretreated if desired. For example, a pillaredbentonite is pretreated by drying at about 300° C. under an inertatmosphere, typically dry nitrogen, for about 3 hours, before beingadded to the polymerization reactor. Although an exemplary pretreatmentis described herein, it should be understood that the preheating can becarried out at many other temperatures and times, including anycombination of temperature and time steps, all of which are encompassedby this disclosure.

The activator-support used to prepare the catalyst compositions of thepresent disclosure can be combined with other inorganic supportmaterials, including, but not limited to, zeolites, inorganic oxides,phosphated inorganic oxides, and the like. In one aspect, typicalsupport materials that are used include, but are not limited to, silica,silica-alumina, alumina, titania, zirconia, magnesia, boria, thoria,aluminophosphate, aluminum phosphate, silica-titania, coprecipitatedsilica/titania, mixtures thereof, or any combination thereof. In anembodiment, the activator-support comprises a sulfated solid oxideactivator support (SSA).

The process of making these activator-supports may includeprecipitation, co-precipitation, impregnation, gelation, pore-gelation,calcining (at up to 900° C.), spray-drying, flash-drying, rotary dryingand calcining, milling, sieving, and similar operations.

In an embodiment, the CATCOMP optionally comprises a metal alkyl or ametalloid alkyl which may function as a cocatalyst. Generally, the metalalkyl compound which can be utilized in the catalyst system of thisdisclosure can be any heteroleptic or homoleptic metal alkyl compound.In an embodiment, the metal alkyl can comprise, consist essentially of,or consist of, a non-halide metal alkyl, a metal alkyl halide, or anycombination thereof; alternatively, a non-halide metal alkyl; oralternatively, a metal alkyl halide.

In an embodiment, the metal of the metal alkyl can comprise, consistessentially of, or consist of, a group 1, 2, 11, 12, 13, or 14 metal; oralternatively, a group 13 or 14 metal; or alternatively, a group 13metal. In some embodiments, the metal of the metal alkyl (non-halidemetal alkyl or metal alkyl halide) can be lithium, sodium, potassium,rubidium, cesium, beryllium, magnesium, calcium, strontium, barium,zinc, cadmium, boron, aluminum, or tin; alternatively, lithium, sodium,potassium, magnesium, calcium, zinc, boron, aluminum, or tin;alternatively, lithium, sodium, or potassium; alternatively, magnesium,calcium; alternatively, lithium; alternatively, sodium; alternatively,potassium; alternatively, magnesium; alternatively, calcium;alternatively, zinc; alternatively, boron; alternatively, aluminum; oralternatively, tin. In some embodiments, the metal alkyl (non-halidemetal alkyl or metal alkyl halide) can comprise, consist essentially of,or consist of, a lithium alkyl, a sodium alkyl, a magnesium alkyl, aboron alkyl, a zinc alkyl, or an aluminum alkyl. In some embodiments,the metal alkyl (non-halide metal alkyl or metal alkyl halide) cancomprise, consist essentially of, or consist of, an aluminum alkyl.

In an embodiment, the aluminum alkyl can be a trialkylaluminum, analkylaluminum halide, an alkylaluminum alkoxide, an aluminoxane, or anycombination thereof. In some embodiments, the aluminum alkyl can be atrialkylaluminum, an alkylaluminum halide, an aluminoxane, or anycombination thereof; or alternatively, a trialkylaluminum, analuminoxane, or any combination thereof. In other embodiments, thealuminum alkyl can be a trialkylaluminum; alternatively, analkylaluminum halide; alternatively, an alkylaluminum alkoxide; oralternatively, an aluminoxane.

In a non-limiting embodiment, the aluminoxane can have a repeating unitcharacterized by the Formula I:

wherein R′ is a linear or branched alkyl group. Alkyl groups for metalalkyls have been independently described herein and can be utilizedwithout limitation to further describe the aluminoxanes having FormulaI. Generally, n of Formula I is greater than 1; or alternatively,greater than 2. In an embodiment, n can range from 2 to 15; oralternatively, range from 3 to 10. In an aspect, each halide of anymetal alkyl halide disclosed herein can independently be fluoride,chloride, bromide, or iodide; alternatively, chloride, bromide, oriodide. In an embodiment, each halide of any metal alkyl halidedisclosed herein can be fluoride; alternatively, chloride;alternatively, bromide; or alternatively, iodide.

In an aspect, the alkyl group of any metal alkyl disclosed herein(non-halide metal alkyl or metal alkyl halide) can each independently bea C₁ to C₂₀ alkyl group; alternatively, a C₁ to C₁₀ alkyl group; oralternatively, a C₁ to C₆ alkyl group. In an embodiment, the alkylgroup(s) can each independently be a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group, a hexyl group, a heptylgroup, or an octyl group; alternatively, a methyl group, a ethyl group,a butyl group, a hexyl group, or an octyl group. In some embodiments,the alkyl group can each independently be a methyl group, an ethylgroup, an n-propyl group, an n-butyl group, an iso-butyl group, ann-hexyl group, or an n-octyl group; alternatively, a methyl group, anethyl group, an n-butyl group, or an iso-butyl group; alternatively, amethyl group; alternatively, an ethyl group; alternatively, an n-propylgroup; alternatively, an n-butyl group; alternatively, an iso-butylgroup; alternatively, an n-hexyl group; or alternatively, an n-octylgroup.

In an aspect, the alkoxide group of any metal alkyl alkoxide disclosedherein can each independently be a C₁ to C₂₀ alkoxy group;alternatively, a C₁ to C₁₀ alkoxy group; or alternatively, a C₁ to C₆alkoxy group. In an embodiment, each alkoxide group of any metal alkylalkoxide disclosed herein can each independently be a methoxy group, anethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxygroup, a heptoxy group, or an octoxy group; alternatively, a methoxygroup, a ethoxy group, a butoxy group, a hexoxy group, or an octoxygroup. In some embodiments, each alkoxide group of any metal alkylalkoxide disclosed herein can each independently be a methoxy group, anethoxy group, an n-propoxy group, an n-butoxy group, an iso-butoxygroup, an n-hexoxy group, or an n-octoxy group; alternatively, a methoxygroup, an ethoxy group, an n-butoxy group, or an iso-butoxy group;alternatively, a methoxy group; alternatively, an ethoxy group;alternatively, an n-propoxy group; alternatively, an n-butoxy group;alternatively, an iso-butoxy group; alternatively, an n-hexoxy group; oralternatively, an n-octoxy group.

In a non-limiting embodiment, useful metal alkyls can include methyllithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, diethylmagnesium, di-n-butylmagnesium, ethylmagnesium chloride,n-butylmagnesium chloride, and diethyl zinc.

In a non-limiting embodiment, useful trialkylaluminum compounds caninclude trimethylaluminum, triethylaluminum, tripropylaluminum,tributylaluminum, trihexylaluminum, trioctylaluminum, or mixturesthereof. In some non-limiting embodiments, trialkylaluminum compoundscan include trimethylaluminum, triethylaluminum, tripropylaluminum,tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum,tri-n-octylaluminum, or mixtures thereof; alternatively,triethylaluminum, tri-n-butylaluminum, tri-isobutylaluminum,trihexylaluminum, tri-n-octylaluminum, or mixtures thereof;alternatively, triethylaluminum, tri-n-butylaluminum, trihexylaluminum,tri-n-octylaluminum, or mixtures thereof. In other non-limitingembodiments, useful trialkylaluminum compounds can includetrimethylaluminum; alternatively, triethylaluminum; alternatively,tripropylaluminum; alternatively, tri-n-butylaluminum; alternatively,tri-isobutylaluminum; alternatively, trihexylaluminum; or alternatively,tri-n-octylaluminum.

In a non-limiting embodiment, useful alkylaluminum halides can includediethylaluminum chloride, diethylaluminum bromide, ethylaluminumdichloride, ethylaluminum sesquichloride, and mixtures thereof. In somenon-limiting embodiments, useful alkylaluminum halides can includediethylaluminum chloride, ethylaluminum dichloride, ethylaluminumsesquichloride, and mixtures thereof. In other non-limiting embodiments,useful alkylaluminum halides can include diethylaluminum chloride;alternatively, diethylaluminum bromide; alternatively, ethylaluminumdichloride; or alternatively, ethylaluminum sesquichloride.

In a non-limiting embodiment, useful aluminoxanes can includemethylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane(MMAO), n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof; Insome non-limiting embodiments, useful aluminoxanes can includemethylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, t-butyl aluminoxane, or mixtures thereof. In othernon-limiting embodiments, useful aluminoxanes can includemethylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively,modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane;alternatively, iso-propylaluminoxane; alternatively, n-butylaluminoxane;alternatively, sec-butylaluminoxane; alternatively,iso-butylaluminoxane; alternatively, t-butyl aluminoxane; alternatively,1-pentylaluminoxane; alternatively, 2-pentylaluminoxane; alternatively,3-pentylaluminoxane; alternatively, iso-pentylaluminoxane; oralternatively, neopentylaluminoxane.

In an embodiment, the metal alkyl comprises comprise an organoboroncompound or an organoborate compound. Organoboron or organoboratecompounds include neutral boron compounds, borate salts, and the like,or combinations thereof. For example, fluoroorgano boron compounds andfluoroorgano borate compounds are contemplated.

Any fluoroorgano boron or fluoroorgano borate compound can be utilizedwith the present disclosure. Examples of fluoroorgano borate compoundsthat can be used in the present disclosure include, but are not limitedto, fluorinated aryl borates such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like, ormixtures thereof. Examples of fluoroorgano boron compounds that can beused in the present disclosure include, but are not limited to,tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,and the like, or mixtures thereof. Although not intending to be bound bythe following theory, these examples of fluoroorgano borate andfluoroorgano boron compounds, and related compounds, are thought to form“weakly-coordinating” anions when combined with organometal compounds,as disclosed in U.S. Pat. No. 5,919,983, the disclosure of which isincorporated herein by reference in its entirety. Applicants alsocontemplate the use of diboron, or bis-boron, compounds or otherbifunctional compounds containing two or more boron atoms in thechemical structure, such as disclosed in J. Am. Chem. Soc., 2005, 127,pp. 14756-14768, the content of which is incorporated herein byreference in its entirety.

In one aspect, the weight ratio of the treated solid oxide component tothe CATCOMP (e.g., metal salt complex prepared from an imine phenolcompound and MTE-A or metal salt complex prepared from an imine-phenolcompound and MTE-B) may be from about 10,000:1 to about 10:1. In anotheraspect, the weight ratio of the treated solid oxide component to theCATCOMP may be from about 5000:1 to about 10:1, an in yet anotheraspect, from about 2000:1 to 50:1. These weight ratios are based on thecombined weights of cocatalyst (e.g., organoaluminum, treated oxide) andCATCOMP used to prepare the catalyst composition, regardless of theorder of contacting the catalyst components. In an embodiment, the metalsalt complex of an imine phenol compound and the metallocene complex arepresent in the CATCOMP in a ratio of from about 100:1 to about 1:100based on the total weight of the CATCOMP, alternatively from about 20:1to about 1:20, or alternatively from about 10:1 to about 1:10.

In an embodiment, CATCOMPs of the type disclosed herein display acatalytic activity in a polymerization reaction ranging from about 1 gPE/g cat·h to about 1,000,000 kg PE/g cat·h, alternatively from about 1kg PE/g cat·h to about 100,000 kg PE/g cat·h, or alternatively fromabout 10 kg PE/g cat·h to about 10,000 kg PE/g cat·h. Catalyst systemactivity is defined as grams of a product produced per gram of thetransition metal salt complex utilized in the catalyst system over thefirst 30 minutes of a reaction beginning from the time when the completecatalyst system is contacted with the olefin. Catalyst system activitycan be stated in terms of various products of an olefin oligomerizationor polymerization.

In an embodiment, a catalyst system of the type disclosed herein is usedto prepare a polymer by any olefin polymerization method, using varioustypes of polymerization reactors. As used herein, “polymerizationreactor” includes any reactor capable of polymerizing olefin monomers toproduce homopolymers and/or copolymers. Homopolymers and/or copolymersproduced in the reactor may be referred to as resin and/or polymers. Thevarious types of reactors include, but are not limited to those that maybe referred to as batch, slurry, gas-phase, solution, high pressure,tubular, autoclave, or other reactor and/or reactors. Gas phase reactorsmay comprise fluidized bed reactors or staged horizontal reactors.Slurry reactors may comprise vertical and/or horizontal loops. Highpressure reactors may comprise autoclave and/or tubular reactors.Reactor types may include batch and/or continuous processes. Continuousprocesses may use intermittent and/or continuous product discharge ortransfer. Processes may also include partial or full direct recycle ofun-reacted monomer, un-reacted comonomer, catalyst and/or co-catalysts,diluents, and/or other materials of the polymerization process.Polymerization reactor systems of the present disclosure may compriseone type of reactor in a system or multiple reactors of the same ordifferent type, operated in any suitable configuration. Production ofpolymers in multiple reactors may include several stages in at least twoseparate polymerization reactors interconnected by a transfer systemmaking it possible to transfer the polymers resulting from the firstpolymerization reactor into the second reactor. Alternatively,polymerization in multiple reactors may include the transfer, eithermanual or automatic, of polymer from one reactor to subsequent reactoror reactors for additional polymerization. Alternatively, multi-stage ormulti-step polymerization may take place in a single reactor, whereinthe conditions are changed such that a different polymerization reactiontakes place.

The desired polymerization conditions in one of the reactors may be thesame as or different from the operating conditions of any other reactorsinvolved in the overall process of producing the polymer of the presentdisclosure. Multiple reactor systems may include any combinationincluding, but not limited to multiple loop reactors, multiple gas phasereactors, a combination of loop and gas phase reactors, multiple highpressure reactors or a combination of high pressure with loop and/or gasreactors. The multiple reactors may be operated in series or inparallel. In an embodiment, any arrangement and/or any combination ofreactors may be employed to produce the polymer of the presentdisclosure.

According to one embodiment, the polymerization reactor system maycomprise at least one loop slurry reactor. Such reactors may comprisevertical or horizontal loops. Monomer, diluent, catalyst system, andoptionally any comonomer may be continuously fed to a loop slurryreactor, where polymerization occurs. Generally, continuous processesmay comprise the continuous introduction of a monomer, a catalyst,and/or a diluent into a polymerization reactor and the continuousremoval from this reactor of a suspension comprising polymer particlesand the diluent. Reactor effluent may be flashed to remove the liquidsthat comprise the diluent from the solid polymer, monomer and/orcomonomer. Various technologies may be used for this separation stepincluding but not limited to, flashing that may include any combinationof heat addition and pressure reduction; separation by cyclonic actionin either a cyclone or hydrocyclone; separation by centrifugation; orother appropriate method of separation.

Typical slurry polymerization processes (also known as particle-formprocesses) are disclosed in U.S. Pat. Nos. 3,248,179, 4,501,885,5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833,415, for example;each of which are herein incorporated by reference in their entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under reaction conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. No. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another embodiment, the polymerization reactor maycomprise at least one gas phase reactor. Such systems may employ acontinuous recycle stream containing one or more monomers continuouslycycled through a fluidized bed in the presence of the catalyst underpolymerization conditions. A recycle stream may be withdrawn from thefluidized bed and recycled back into the reactor. Simultaneously,polymer product may be withdrawn from the reactor and new or freshmonomer may be added to replace the polymerized monomer. Such gas phasereactors may comprise a process for multi-step gas-phase polymerizationof olefins, in which olefins are polymerized in the gaseous phase in atleast two independent gas-phase polymerization zones while feeding acatalyst-containing polymer formed in a first polymerization zone to asecond polymerization zone. One type of gas phase reactor is disclosedin U.S. Pat. Nos. 4,588,790, 5,352,749, and 5,436,304, each of which isincorporated by reference in its entirety herein.

According to still another embodiment, a high pressure polymerizationreactor may comprise a tubular reactor or an autoclave reactor. Tubularreactors may have several zones where fresh monomer, initiators, orcatalysts are added. Monomer may be entrained in an inert gaseous streamand introduced at one zone of the reactor. Initiators, catalysts, and/orcatalyst components may be entrained in a gaseous stream and introducedat another zone of the reactor. The gas streams may be intermixed forpolymerization. Heat and pressure may be employed appropriately toobtain optimal polymerization reaction conditions.

According to yet another embodiment, the polymerization reactor maycomprise a solution polymerization reactor wherein the monomer iscontacted with the catalyst composition by suitable stirring or othermeans. A carrier comprising an organic diluent or excess monomer may beemployed. If desired, the monomer may be brought in the vapor phase intocontact with the catalytic reaction product, in the presence or absenceof liquid material. The polymerization zone is maintained attemperatures and pressures that will result in the formation of asolution of the polymer in a reaction medium. Agitation may be employedto obtain better temperature control and to maintain uniformpolymerization mixtures throughout the polymerization zone. Adequatemeans are utilized for dissipating the exothermic heat ofpolymerization.

Polymerization reactors suitable for the present disclosure may furthercomprise any combination of at least one raw material feed system, atleast one feed system for catalyst or catalyst components, and/or atleast one polymer recovery system. Suitable reactor systems for thepresent invention may further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Conditions that are controlled for polymerization efficiency and toprovide polymer properties include, but are not limited to temperature,pressure, type and quantity of catalyst or co-catalyst, and theconcentrations of various reactants. Polymerization temperature canaffect catalyst productivity, polymer molecular weight and molecularweight distribution. Suitable polymerization temperatures may be anytemperature below the de-polymerization temperature, according to theGibbs Free Energy Equation. Typically, this includes from about 60° C.to about 280° C., for example, and/or from about 70° C. to about 110°C., depending upon the type of polymerization reactor and/orpolymerization process.

Suitable pressures will also vary according to the reactor andpolymerization process. The pressure for liquid phase polymerization ina loop reactor is typically less than 1000 psig. Pressure for gas phasepolymerization is usually at about 200-500 psig. High pressurepolymerization in tubular or autoclave reactors is generally run atabout 20,000 to 75,000 psig. Polymerization reactors can also beoperated in a supercritical region occurring at generally highertemperatures and pressures. Operation above the critical point of apressure/temperature diagram (supercritical phase) may offer advantages.

The concentration of various reactants can be controlled to producepolymers with certain physical and mechanical properties. The proposedend-use product that will be formed by the polymer and the method offorming that product may be varied to determine the desired finalproduct properties. Mechanical properties include, but are not limitedto tensile strength, flexural modulus, impact resistance, creep, stressrelaxation and hardness tests. Physical properties include, but are notlimited to density, molecular weight, molecular weight distribution,melting temperature, glass transition temperature, temperature melt ofcrystallization, density, stereoregularity, crack growth, short chainbranching, long chain branching and rheological measurements.

The concentrations of monomer, co-monomer, hydrogen, co-catalyst,modifiers, and electron donors are generally important in producingspecific polymer properties. Comonomer may be used to control productdensity. Hydrogen may be used to control product molecular weight.Co-catalysts may be used to alkylate, scavenge poisons and/or controlmolecular weight. The concentration of poisons may be minimized, aspoisons may impact the reactions and/or otherwise affect polymer productproperties. Modifiers may be used to control product properties andelectron donors may affect stereoregularity.

In an embodiment, the CATCOMP comprises a metal salt prepared from animine phenol compound characterized by Structure XV, a metallocenecompound characterized by Structure 15 or Structure 18, a sulfated solidoxide of the type disclosed herein and an alkylaluminum complex of thetype disclosed herein.

The CATCOMP can be contacted with a monomer (e.g., ethylene and optionalcomonomer) under conditions suitable for the formation of a polymer(e.g., polyethylene). In an embodiment, a monomer (e.g., ethylene) ispolymerized using the methodologies disclosed herein to produce apolymer. The polymer may comprise a homopolymer, a copolymer, orcombinations thereof. In an embodiment, the polymer is a copolymercomprising ethylene and one or more comonomers such as, for example,alpha olefins. Examples of suitable comonomers include, but are notlimited to, unsaturated hydrocarbons having from 3 to 20 carbon atomssuch as propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, andmixtures thereof. In an embodiment, the comonomer is 1-hexene. In anembodiment, the commoner may be present in the polymer in an amount ofequal to or less than about 0.5 mol. %, alternatively less than about0.4 mol. %, alternatively less than about 0.3 mol. % or alternativelyless than about 0.2 mol. %. In an embodiment, the polymer is ahomopolymer. It is to be understood that an inconsequential amount ofcomonomer may be present in the polymers disclosed herein and thepolymer still be considered a homopolymer. Herein an inconsequentialamount of a comonomer refers to an amount that does not substantivelyaffect the properties of the polymer disclosed herein.

The polymer may include other additives. Examples of additives include,but are not limited to, antistatic agents, colorants, stabilizers,nucleators, surface modifiers, pigments, slip agents, antiblocks,tackafiers, polymer processing aids, and combinations thereof. Suchadditives may be used singularly or in combination and may be includedin the polymer before, during, or after preparation of the polymer asdescribed herein. Such additives may be added via any suitabletechnique, for example during an extrusion or compounding step such asduring pelletization or subsequent processing into an end use article.

In an embodiment, a polymer of the type described herein is atwo-component system comprising a first component designated Component Aand a second component designated Component B. The polymer may be areactor-blend that is result of the use a catalyst system of the typedisclosed herein (i.e., a metal complex prepared from an iminebis(phenol) compound, a metallocene) where the polymer is formed bypolymerization of a monomer (e.g., olefin) in the presence of thecatalyst system and a metal alkyl, all of the type disclosed herein. Inan embodiment, Component A and Component B possess an overlappingmolecular weight distribution profile such that the MWD profile ofComponent B is encompassed by the MWD profile of Component A. ComponentA may have a polymer architecture that is characterized by a broad MWD,high-density and is substantially linear. Component B may have a polymerarchitecture that is characterized by a narrow MWD and increasedbranching when compared to Component A. Each of these characteristicsare described in more detail later herein. Component A may be present inan amount that constitutes from about 1 weight percent (wt. %) to about99 wt. % based on the total weight of the polymer, alternatively fromabout 10 wt. % to about 90 wt. % or alternatively from about 20 wt. % toabout 80 wt. %. In an embodiment, greater than about 90%, 91, 92, 93,94, 95, 96, 97, 98, or 99% of the remainder of the polymer comprisesComponent B.

In an embodiment, Component A is characterized by a density of fromabout 0.94 g/cc to about 0.98 g/cc, alternatively from about 0.95 g/ccto about 0.980 g/cc, or alternatively from about 0.955 g/cc to about0.980 g/cc as determined in accordance with ASTM D-1505. Component B maybe characterized by a density of from about 0.86 g/cc to about 0.98g/cc, alternatively from about 0.87 g/cc to about 0.97 g/cc, oralternatively from about 0.88 g/cc to about 0.96 g/cc as determined inaccordance with ASTM D-1505.

In an embodiment, a polymer of the type described herein is multimodal.Herein, the “modality” of a polymer refers to the form of its molecularweight distribution curve, i.e. the appearance of the graph of thepolymer weight fraction as a function of its molecular weight. Thepolymer weight fraction refers to the weight fraction of molecules of agiven size. A polymer having a molecular weight distribution curveshowing a single peak may be referred to as a unimodal polymer, apolymer having curve showing two distinct peaks may be referred to asbimodal polymer, a polymer having a curve showing three distinct peaksmay be referred to as trimodal polymer, a polymer having a curve showingtwo or more peaks may be referred to as multimodal, etc. Polymermodality may be determined using any suitable methodology such as thosedescribed in the examples sections herein.

In an embodiment, a polymer of the type described herein may have aweight average molecular weight (M_(w)) for Component A ranging fromabout 50 kg/mol to about 1000 kg/mol, alternatively from about 100kg/mol to about 750 kg/mol or alternatively from about 200 kg/mol toabout 500 kg/mol while component B may have a M_(w) ranging from about20 kg/mol to about 2000 kg/mol, alternatively from about 50 kg/mol toabout 1500 kg/mol or alternatively from about 100 kg/mol to about 1000kg/mol. The M, for the polymer composition as a whole may range fromabout 50 kg/mol to about 1000 kg/mol, alternatively from about 75 kg/molto about 750 kg/mol, alternatively from about 100 kg/mol to about 500kg/mol. The weight average molecular weight describes the molecularweight distribution of a polymer and is calculated according to Equation1:

$\begin{matrix}{M_{w} = \frac{\sum_{i}{N_{i}M_{i}^{2}}}{\sum_{i}{N_{i}M_{i}}}} & (1)\end{matrix}$where N_(i) is the number of molecules of molecular weight M_(i).

The M_(n) for the polymer composition as a whole may range from about 1kg/mol to about 100 kg/mol, alternatively from about 5 kg/mol to about50 kg/mol, alternatively from about 10 kg/mol to about 30 kg/mol. Thenumber average molecular weight is the common average of the molecularweights of the individual polymers and may be calculated according toEquation 2:

$\begin{matrix}{M_{n} = \frac{\sum_{i}{N_{i}M_{i}}}{\sum_{i}N_{i}}} & (2)\end{matrix}$where N_(i) is the number of molecules of molecular weight M_(i).

A polymer of the type disclosed herein may be characterized by a peakmolecular weight (M_(p)) of from about 10 kg/mol to about 1000 kg/mol,alternatively from about 50 kg/mol to about 500 kg/mol, or alternativelyfrom about 50 kg/mol to about 400 kg/mol. The M_(p) refers to themolecular weight of the highest and is a mode of the MWD.

In an embodiment, a polymer of the type described herein may becharacterized by a MWD for Component A of greater than about 20,alternatively greater than about 25, or alternatively greater than about30 while Component B may be characterized by a MWD of less than about20, alternatively less than about 15, alternatively less than about 10,or alternatively less than about 5. A polymer of the type describedherein, as a whole, may be characterized by a MWD of from about 3 toabout 100, alternatively from about 6 to about 75, or alternatively fromabout 10 to about 50. The MWD is the ratio of the M_(w) to the numberaverage molecular weight (M_(n)), which is also referred to as thepolydispersity index (PDI) or more simply as polydispersity.

A polymer of the type described herein may be further characterized by aratio of z-average molecular weight (M_(z)) to M_(w) (M_(z)/M_(w)) offrom about 1.5 to about 20, alternatively from about 2 to about 15 oralternatively from about 3 to about 10. The z-average molecular weightis a higher order molecular weight average which is calculated accordingto Equation 3:

$\begin{matrix}{M_{z} = \frac{\sum_{i}{N_{i}M_{i}^{3}}}{\sum_{i}{N_{i}M_{i}^{2}}}} & (3)\end{matrix}$where N_(i) is the amount of substance of species i and M_(i) is themolecular weight of species i. The ratio of M_(z)/M_(w) is anotherindication of the breadth of the MWD of a polymer.

In an embodiment, a polymer of the type described herein may have a highload melt index, HLMI, in a range from about 0.01 g/10 min. to about1000 g/10 min., alternatively from about 0.1 g/10 min. to about 100 g/10min., or alternatively from about 1 g/10 min. to about 20 g/10 min. Thehigh load melt index (HLMI) refers to the rate a polymer which can beforced through an extrusion rheometer orifice of 0.0824 inch diameterwhen subjected to a force of 21,600 grams at 190° C. in accordance withASTM D 1238.

In an embodiment, a polymer of the type disclosed herein has a CarreauYasuda ‘a’ parameter, CY-a, in the range of from about 0.05 to about0.8, alternatively from about 0.1 to about 0.5, or alternatively fromabout 0.15 to about 0.4. The Carreau Yasuda ‘a’ parameter (CY-a) isdefined as the rheological breath parameter. Rheological breadth refersto the breadth of the transition region between Newtonian and power-lawtype shear rate for a polymer or the frequency dependence of theviscosity of the polymer. The rheological breadth is a function of therelaxation time distribution of a polymer resin, which in turn is afunction of the resin molecular structure or architecture. The CY-aparameter may be obtained by assuming the Cox-Merz rule and calculatedby fitting flow curves generated in linear-viscoelastic dynamicoscillatory frequency sweep experiments with a modified Carreau-Yasuda(CY) model, which is represented by Equation (4):

$\begin{matrix}{E = {E_{o}\left\lbrack {1 + \left( {T_{\xi}\overset{.}{\gamma}} \right)^{a}} \right\rbrack}^{\frac{n - 1}{a}}} & (4)\end{matrix}$

where

E=viscosity (Pa·s)

{dot over (γ)}=shear rate (1/s)

a=rheological breadth parameter

T_(ξ)=relaxation time (s) [describes the location in time of thetransition region]

E_(o)=zero shear viscosity (Pa·s) [defines the Newtonian plateau]

n=power law constant [defines the final slope of the high shear rateregion]

To facilitate model fitting, the power law constant n is held at aconstant value. Details of the significance and interpretation of the CYmodel and derived parameters may be found in: C. A. Hieber and H. H.Chiang, Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang,Polym. Eng. Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O.Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2ndEdition, John Wiley & Sons (1987), each of which is incorporated byreference herein in its entirety.

In an embodiment, a polymer of the type described herein may have azero-shear viscosity (η₀) of from about 1E+03 Pa-s to about 1E+10 Pa-s,alternatively from about 1E+04 Pa-s to about 1E+09 Pa-s, oralternatively from about 1E+05 Pa-s to about 1E+08 Pa-s.

In an embodiment, a polymer of the type disclosed herein is furthercharacterized by a reverse comonomer branching distribution or reverseshort-chain branching distribution (SCBD) resulting in short-chainbranching (SCB) that occurs primarily in Component B of the polymer.Herein, the SCBD refers to number of SCB per 1000 carbon atoms at eachMW across the MWD profile of a polymer.

In an embodiment, a polymer of the type disclosed herein ischaracterized by a short-chain branching content of from about 0.1 toabout 20 short chain branches per 1000 total carbon atoms, alternativelyfrom about 0.5 to about 15, or alternatively from about 1 to about 10.In another embodiment, a polymer of the type disclosed herein ischaracterized by the SCB present in Component B in an amount thatconstitutes from about 75% to about 100% based on the number ofshort-chain branches per 1000 carbon atoms, alternatively from about 80%to about 100% based on the number of short-chain branches per 1000carbon atoms, alternatively from about 90% to about 100% based on thenumber of short-chain branches per 1000 carbon atoms.

In an embodiment, a polymer of the type disclosed herein is a reactorblend of polymers prepared by contacting metal salt prepared from animine bis(phenol) compound, a metallocene compound and a metal alkyl,all of the type disclosed herein, with a monomer under conditionssuitable for the for formation of a polymer. In an embodiment, themonomer is ethylene. Alternatively the polymer formed comprises ethyleneand 1-hexene. In an embodiment, the polymer has a polydispersity indexof greater than about 15 and a short-chain branching distributionmaximum that occurs between a weight average molecular weight of about30 kDa and 1000 kDa. In an embodiment, the polymer has a level ofshort-chain branching ranging from about 0.1 to about 20 short chainbranches per 1000 total carbon atoms, alternatively from about 0.5 toabout 15 or alternatively from about 1 to about 10.

Polymers of the type disclosed herein may be characterized by a shortchain branching distribution that is described by a Pearson VII Ampcurve fit wherein the value of the short chain branching distributionslope from the short chain branching distribution maximum at a log ofthe weight average molecular weight less than about the maximum logweight average molecular weight is less than about −0.005. The PearsonAmp Curve Fit is based on the Pearson VII model which contains fouradjustable parameters a, p, q, and v0 which correspond to amplitude,line width, shape factor and band center respectively. As q→1 the bandreduces to a Lorenzian distribution and as q approaches 50 a more orless Gaussian distribution is obtained. Thus, the Pearson VIIcurve-fitting procedure approximates a mixed Lorentzian-Gaussian modelfor band shape.

Polymers of the type disclosed herein may be formed into articles ofmanufacture or end-use articles using techniques known in the art suchas extrusion, blow molding, injection molding, fiber spinning,thermoforming, and casting. Polymers of the type disclosed herein maydisplay an improved processability.

In an embodiment, the polymer comprises PE which may be fabricated intoa pipe by extrusion. Extrusion refers to a method of making a polymericpipe comprising extruding the polymer or copolymer in a molten statethrough a die to cool and form the polymeric pipe. Hereinafter thedisclosure will refer to PE pipe although other polymeric articles arealso contemplated.

Pipe extrusion in the simplest terms is performed by conveying solidpolymer pellets through the action of a rotating screw followed by thecompaction and melting of the pellets through the application of heatand shear forces; the homogenous polymer melt is then conveyed to thedie to form the ultimately desired profile. For the fabrication of pipesthe extrudate (melt exiting the die), which is annular in shape, is thenformed and cooled through a series of vacuum and water cooling tanks.There are numerous kinds of feedstocks in pipe extrusion. The polymerfeedstock can either be a pre-pigmented polyethylene resin or it can bea mixture of natural polyethylene and color concentrate (referred to as“Salt and Pepper blends”). In North America, the most common feedstockfor pipe extrusion is “Salt and Pepper blends”. In Europe and otherareas of the world, the most common feedstock for pipe extrusion ispre-pigmented polyethylene resin. Feedstock is rigidly controlled toobtain the proper finished product (pipe) and ultimate consumerspecifications. In one “salt and pepper blend” embodiment, the colorconcentrate is a polyethylene carrier resin loaded with up to 40 weightpercent carbon black particles; this concentrate is introduced tomaintain approximately 2.5 weight percent carbon black concentration inthe final pipe.

The feedstock is then fed into an extruder. The most common extrudersystem for pipe production is a single-screw extruder. The purpose ofthe extruder is to melt, homogenize and convey the polyethylene pellets.Extrusion temperatures typically range from 170° C. to 260° C. dependingupon the extruder screw design and flow properties of the polyethylene.

The molten polymer is then passed through an annular die to shape themelt. The molten polymer, in the form of an annulus, is then usuallyforced through a shaping or forming tank while simultaneously beingcooled from the outside using a water spray. While the pipe diameter isa direct consequence of the die and sizing sleeve dimensions, the pipewall thickness depends on the die gap and also the draw-down speedemployed.

Next, the pipe is cooled and solidified in the desired dimensions.Cooling is accomplished by the use of several water tanks where theoutside pipe is either submerged in water or water is sprayed on thepipe exterior. The pipe is cooled from the outside surface to the insidesurface. The interior wall and inside surfaces of the pipe can stay hotfor a long period of time, as polyethylene is a poor conductor of heat.Finally, the pipe is printed and either coiled or cut to length.

In an embodiment, the PE pipes of this disclosure display enhancedmechanical properties such as resistance to slow crack growth, decreasedtensile natural draw ratio (NDR), resistance to rapid crack propagationand strength sufficient to warrant the designation PE100. Thedesignation PE100 refers to a pressure rating wherein the pipe has aminimum required strength value (50 year extrapolated value at 20° C.;97.5 lower prediction limit) equal to or greater than 10.0 MPa. Suchpipes may display the properties described below either singularly or incombination. The specific methods for determination of these propertiesare described in more detail herein.

A majority of the field failures in pressure pipe applications areattributable to slow crack growth (SCG). This has led to the developmentof many lab-scale tests, such as the Pennsylvania Edge-Notch TensileTest (PENT; ASTM F1473), to predict the resistance to SCG of variouspolyethylenes. In the PENT test, a notched polyethylene specimen issubjected to creep by the application of a constant tensile load at 80°C. The applied load is such that the initial stress is 3.8 MPa. The timeto failure is recorded and reported. A longer failure time correlateswith a greater resistance to SCG. Generally speaking, increasing theresin density lowers the PENT failure times. The PE pipe of the typedisclosed herein may display PENT failure times of greater than about800 hours (h) to about 2000 hours, alternatively greater than about 1500h, or alternatively greater than about 2000 h.

Since the majority of field failures in pressure pipe (gas transport)applications are attributable to a brittle fracture mode referred to asSCG, the resistance to SCG of pressure pipe is often evaluated. Onemethod of evaluating the SCG resistance is by determining the tensilenatural draw ratio (tensile NDR) of the resin. There is some evidencethat the tensile NDR is directly related to the SCG resistance of HDPEsuch that the lower the tensile NDR the higher the resistance to SCG. Adescription of the correlation of SCG to tensile NDR may be found in: E.Laurent, Comprehensive Evaluation of the Long-Term Mechanical Propertiesof PE100 Resin Meeting the Requirements of Modern InstallationTechniques, Plastic Pipes XI Proceedings of the InternationalConference, Woodhead Publishing Limited (2001); and in an article by L.Hubert, et al published in 2002 in the Journal of Applied PolymerScience Volume 84 page 2308 each of which is incorporated herein byreference herein in its entirety.

The tensile NDR is determined by performing standard tensilestress-strain experiments on dogbone specimens at a deformation rate of51 mm/min in accordance with ASTM D638. Referring to FIG. 1, arepresentative stress-strain curve is shown where the tensile strain isplotted as percent strain and the stress is expressed as force or load(in lbf). Inflection points 20, 40, 50 and 60 mark points at whichtransformations in material behavior occur. Initially, at conditions oflow strain a linear region 10 is observed. In this linear region 10 thematerial experiences a stress (F) directly proportional to the appliedstrain (u) and the material behavior can be approximated by Hooke's law(equation 5) with the constant of proportionality being the elastic orYoung's modulus denoted Y:F=Yu  (5)

Also, in the linear region 10, the deformation behavior is approximatelyelastic, i.e. the material strain returns to zero when the applied loadis removed. The stress at the point where the material's behaviorchanges from elastic to plastic is known as the yield stress.Application of a load beyond the yield point 20, results in permanent(or plastic) material deformation. Generally, the yield point 20 inpolyethylene is evident as a maximum in the load-strain traces as shownin FIG. 1. Beyond the yield point, as the specimen is stretchedcontinuously, the material outside the neck region in the dogbonespecimen is drawn into the neck; the load does not change very muchduring this necking and drawing process. This necking/drawing processcontinues until the specimen encounters “strain-hardening” or point 50in FIG. 1. The onset of strain-hardening simply means that any furtherdeformation of the specimen requires considerably more energy input.This is evident in a substantial and dramatic increase in the load inFIG. 1. In other words, the onset of strain hardening 50 marks a period90 when more stress is required to achieve a given strain than seen inthe previous region of the curve. The percent strain at the onset ofstrain-hardening is defined as the tensile NDR. The continuedapplication of load to the material will eventually result in thematerial's fracture at the break stress and strain point 60.

Some polymers do not exhibit the distinct strain-hardening behaviorshown in FIG. 1. Therefore, in order to define a tensile NDR, thefollowing criterion needs to be satisfied first: the tensile stress atbreak is at least 10% higher than that of the tensile yield stress(σ_(brk)>1.10*σ_(y)).

In an embodiment, articles (e.g., pipe) prepared from polymers of thetype disclosed herein have a tensile NDR ranging from about 540% toabout 600%, alternatively less than about of 600% alternatively lessthan about 550% or less than about 540%.

Polymers prepared from CATCOMPs of the type disclosed herein may containsome user and/or process desired SCBD. The SCBD of the polymers may beadjusted by adjusting the composition of the CATCOMP to provide a SCBDthat may be targeted to lie within one or more defined molecular weightranges of the polymer composition.

EXAMPLE

The present disclosure is further illustrated by the following example,which is not to be construed in any way as imposing limitations upon thescope thereof. On the contrary, it is to be clearly understood thatresort can be had to various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, cansuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

The data and descriptions provided in the following example are given toshow particular aspects and embodiments of the subject matter disclosed,and to demonstrate a number of the practices and advantages thereof. Theexample is given as a more detailed demonstration of some of the aspectsand embodiments described herein and is not intended to limit thedisclosure or claims in any manner.

CATCOMPs of the type disclosed herein were utilized in thepolymerization of ethylene. Specifically a CATCOMP comprising the iminebis(phenolate) compound designated Structure XV in Table 1, and ametallocene compound of either Structure 15 or Structure 18 was utilizedto produce nine polyethylene samples, designated Samples S1-S9. Eachsample was prepared from a mixture comprising 1 g of S-SSA, 0.6 ml ofTIBA and a select amount of 1-hexene which was subjected to 450 psi ofethylene monomer and allowed to polymerize at 100° C. for 45 min.

TABLE 1 M_(n)/ M_(w)/ Cat Hy- 1- 1000 1000 Sample Amount PE drogenhexene Density (kg/ (kg/ No. Cat (mg) (g) (ppm) (g) HLMI (g/cc) mol)mol) C1 Structure 3 213 150  5 6.9 0.9656 9.99 356.03 XV S1 Struc-ture3/0.5 311 225  5 5.5 0.9501 15.43 310.19 XV/ Structure 18 S2 Structure3/0.5 280 200  5 4 0.9520 14.79 361.63 XV/ Structure 18 S3 Structure3/0.5 306 175  5 3.2 0.9525 12.74 405.4 XV/ Structure 18 S4 Structure3/0.5 220 165  5 2.2 0.9546 10.98 440.31 XV/ Structure 18 S5 Structure4/0.5 269 225  7 2.2 0.9483 15.71 308.01 XV/ Structure 18 S6 Structure3/0.15 325 225  5 3.9 0.9533 14.94 291.34 XV/ Structure 15 S7 Structure3/0.15 285 200  5 3.4 0.9498 17.64 294.67 XV/ Structure 15 S8 Structure3/0.15 318 175  5 1.8 0.9505 19.3 323.63 XV/ Structure15 S9 Struc ture3/0.2 324 200  5 2.9 0.9488 18.02 291.5 XV/ Structure 15 S10 Structure3/0.2 347 175  5 1.4 0.9462 20.52 317.16 XV/ Structure 15 S11 Structure3/0.2 299 175 10 2.4 0.9445 16.63 265.24 XV/ Structure 15 S12 Structure3/0.3 334 200 10 2.8 0.9405 16.95 239.47 XV/ Structure 15 M_(z)/ M_(v)/M_(p)/ 1000 1000 1000 Sample (kg/ (kg/ (kg/ Mw/ η₀ No. mol) mol) mol) Mn(Pa-s) CY-a C1 2544.2 235.49 53.9 35.64 2.41E+ 0.1722 07 S1 2229.78216.1 78.31 20.1 8.43E+ 0.1414 06 S2 2343.5 252.7 81.29 24.45 8.26E+0.1664 06 S3 2602.86 280.2 92.05 31.82 1.75E+ 0.1672 07 S4 2791.97300.95 113.69 40.1 8.50E+ 0.2152 06 S5 1436.62 231.76 107.23 19.6 3.02E+0.2406 06 S6 1907.37 211.02 99.17 19.5 4.77E+ 0.2580 05 S7 1815.63 217.9116.55 16.7 4.02E+ 0.2571 05 S8 1675.73 245.52 155.04 16.77 5.12E+0.3165 05 S9 1628.36 219.82 121.49 16.18 4.6E+ 0.2720 05 S10 1490.02247.66 160.52 15.46 4.63E+ 0.3199 05 S11 1566.79 202.41 176.72 15.951.62E+ 0.3193 05 S12 1193.32 190.17 154.23 14.13 1.0E+ 0.3646 05

Various properties of the polymer sample are also presented in Table 1.A comparative sample was polymerized in the presence of the iminebis(phenolate) compound represented by Structure XV is designated C1.The data in table 1 demonstrates that by tuning the catalyst compositionand reactor conditions polymer samples having various properties wereproduced. The catalyst combination, amount of 1-hexene, and hydrogenallowed access to a range of HLMIs. Generally, the HLMI of the polymersamples increased with increasing hydrogen feed for a given combinationallowing access to a range of HLMIs. Also generally, the density of thepolymer samples decreased with increasing 1-hexene addition. GPC curvesfor samples S3 and S9 are presented in FIG. 1. The CATCOMPs used toprepared samples S3 and S9 contained the compounds represented byStructures 18 and 15 respectively as the metallocene component. Notablysample S3 displayed a broader MWD, contained a lower M_(p), and a moresubstantial HMW tail. The rheology of polymers of the type disclosedherein was investigated by monitoring the dynamic melt viscosity as afunction of frequency. These results are presented in FIG. 2 for samplesS3 and S9. These results are compared to polymers prepared using a dualmetallocene system, sample C2, or a chromium catalyst, sample C3. Thepolymers of the present disclosure are highly shear thinning, similar tochromium sample C3, suggesting the materials will display relatedprocessability when compared to chromium systems and display a markedimprovement in processability when compared to systems preparedutilizing a dual metallocene catalyst. Chromium sample C3 is thecommercial benchmark resin in melt strength, and in light of thesimilarities in the rheology to S3 and S9, should mean the polymers ofthe present disclosure should display comparable melt strength.

The SCBD of polymers of the type disclosed herein, specifically samplesS3 and S10, were determined by GPC and the results are presented inFIGS. 4 and 5 respectively. The results demonstrate that the butylbranches are located within Component B. The tensile NDR for variouspolymer samples of the type disclosed herein was determined and arepresented in Table 2. As shown in Table 2, the inclusion of theshort-chain branches by the inclusion of the compounds represented byStructures 15 and 18 led to a significant reduction in the NDR (%) andincreased slow crack growth resistance. For example, C1 which wasprepared in the absence of the compounds represented by Structures 15 or18 had an NDR of 747. The inclusion of compounds represented byStructures 15 or 18 in the polymerization both reduced the density andNDR of the polymer.

Comparisons of the polymers of the type disclosed herein (i.e., preparedusing CATCOMPS) to polymers prepared with chromium catalysts C3 and C4are contained in Table 3. The data illustrates improved SCG resistancefor polymers of the type disclosed herein, e.g., S2 and S12, for asimilar density as given by the reduced NDR.

The improved SCG resistance by NDR measurement is demonstrated by thePENT testing in Table 4. At the same density, S5 vastly outperforms C3in PENT.

TABLE 2 Sample No. Density (g/cc) NDR (%) C1 0.966 747.0 S1 0.950 543.8S2 0.952 537.2 S3 0.953 531.8 S4 0.955 517.4 S5 0.948 504.0 S6 0.953580.7 S7 0.950 511.8 S8 0.951 558.7 S9 0.949 518.5 S10 0.946 464.5 S110.945 479.7 S12 0.941 447.7

TABLE 3 Sample No. Density (g/cc) NDR (%) C3 0.947 591 S5 0.948 504 C40.938 507 S12 0.941 448

TABLE 4 Sample No. Density (g/cc) NDR (%) PENT 3.8 MPa (h) C3 0.947 591188 S5 0.948 504 >2000

The results demonstrate the placement of SCB within the HMW end of thebroad distribution provides polymers with superb SCG resistance asindicated by the NDR and PENT values. Comonomer incorporation withpolymers prepared using the CATCOMPs of this disclosure displayedimproved properties such as low NDR values across a range of densities.

The following enumerated embodiments are provided as non-limitingexamples.

A first embodiment, which is a catalyst composition comprising:

(i) a metal salt complex prepared from an imine phenol compoundcharacterized by Structure I:

wherein:

O and N represent oxygen and nitrogen respectively;

R is a halogen, a hydrocarbyl group, or a substituted hydrocarbyl group;

R² and R³ are each independently hydrogen, a halogen, a hydrocarbylgroup, or a substituted hydrocarbyl group; and

Q is a donor group; and

(ii) a metallocene complex.

A second embodiment, which is the composition of the first embodimentwherein the metal salt complex prepared from an imine phenol compoundhas Structure XIV:

where M is a Group 3 to Group 12 transition metal or lanthanide, Et₂O isoptional; and

R and R² are each independently hydrogen, a halogen, a hydrocarbylgroup, or a substituted hydrocarbyl group.

A third embodiment, which is the composition of the first embodimentwherein the metal salt complex prepared from an imine phenol compoundhas structure X:

where Et₂O is optional.

A fourth embodiment, which is the composition of any of the first tothird embodiments wherein the metallocene compound is represented by acompound having general Formula 1 or Formula 2:

where each X is independently F, Cl, Br, I, methyl, benzyl, phenyl, H,BH₄, a hydrocarbyloxide group having up to 20 carbon atoms, ahydrocarbylamino group having up to 20 carbon atoms, atrihydrocarbylsilyl group having up to 20 carbon atoms, OBR′₂ wherein R′is an alkyl group having up to 12 carbon atoms or an aryl group havingup to 12 carbon atoms, and SO₃R″, wherein R″ is an alkyl group having upto 12 carbon atoms or an aryl group having up to 12 carbon atoms; Y is aCR₂ or SiR₂ group where R is hydrogen or a hydrocarbyl group; Cp^(A),Cp^(B), Cp^(C), and Cp^(D) are each independently a substituted orunsubstituted cyclopentadienyl group, indenyl group, or flourenyl groupand where any substituent on Cp^(A), Cp^(B), Cp^(C), and Cp^(D) is H, ahydrocarbyl group having up to 18 carbon atoms or a hydrocarbylsilylgroup having up to 18 carbon atoms.

A fifth embodiment, which is the composition of any of the first tothird embodiments wherein the metallocene compound comprises at leastone of the compounds of Structures 1-13:

A sixth embodiment, which is the composition of any of the first tothird embodiments wherein the metallocene compound is represented by acompound having general Formula 3 or Formula 4:

where M is Ti, Zr or Hf; each X is independently F, Cl, Br, I, methyl,phenyl, benzyl, H, BH₄, a hydrocarbyloxide group having up to 20 carbonatoms, a hydrocarbylamino group having up to 20 carbon atoms, atrihydrocarbylsilyl group having up to 20 carbon atoms, OBR′₂ wherein R′is an alkyl group having up to 12 carbon atoms or an aryl group havingup to 12 carbon atoms, or SO₃R″ wherein R″ is an alkyl group having upto 12 carbon atoms or an aryl group having up to 12 carbon atoms; Y is aCR₂, SiR₂, or R₂CCR₂ group which may be linear or cyclic and where R ishydrogen or a hydrocarbyl group; Cp^(A), Cp^(B), Cp^(C), and Cp^(D) areeach independently a substituted or unsubstituted cyclopentadienylgroup, indenyl group, or flourenyl group and where any substituent onCp^(A), Cp^(B), Cp^(C), and Cp^(D) is H, a hydrocarbyl group having upto 18 carbon atoms or a hydrocarbylsilyl group having up to 18 carbonatoms, E represents a bridging group comprising (i) a cyclic orheterocyclic moiety having up to 18 carbon atoms, (ii) a grouprepresented by the general formula E^(A)R^(3A)R^(4A), wherein E^(A) is Cor Si, and R^(3A) and R^(4A) are independently H or a hydrocarbyl grouphaving up to 18 carbon atoms, (iii) a group represented by the generalformula —CR^(3B)R^(4B)—CR^(3C)R^(4C)—, wherein R^(3B), R^(4B), R^(3C),and R^(4C) are independently H or a hydrocarbyl group having up to 10carbon atoms, or (iv) a group represented by the general formula—SiR^(3D)R^(4D)—SiR^(3E)R^(4E)—, wherein R^(3D), R^(4D), R^(3E), andR^(4E) are independently H or a hydrocarbyl group having up to 10 carbonatoms, and wherein at least one of R^(3A), R^(3B), R^(4A), R^(4B),R^(3C), R^(4C), R^(3D), R^(4D), R^(3E), R^(4E), or the substituent onCp, Cp₁, or Cp₂, is (1) a terminal alkenyl group having up to 12 carbonatoms or (2) a dinuclear compound wherein each metal moiety has the samestructural characteristic.

A seventh embodiment, which is the composition of any of the first tothird embodiments wherein the metallocene compound comprises at leastone of the compounds of Structures 14-29:

An eighth embodiment, which is the composition of any of the precedingembodiments wherein the metal salt complex prepared from an imine phenolcompound and the metallocene complex are present in an amount of fromabout 100:1 to about 1:100 based on the total weight of the catalystcomposition.

A ninth embodiment, which is the composition of any of the precedingembodiments, further comprising a metal alkyl compound.

A tenth embodiment, which is the composition of the ninth embodiment,wherein the metal alkyl compound comprises an organoaluminum compound,an aluminoxane compound, and organoboron or organoborate compound, anionizing ionic compound, or combinations thereof.

An eleventh embodiment, which is the composition of any of the precedingembodiments, further comprising an activator-support comprising a solidoxide treated with an electron-withdrawing anion.

A twelfth embodiment, which is the composition of the eleventhembodiment wherein the solid oxide comprises silica, alumina,silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, a mixed oxide thereof, or combinations thereof; and

the electron-withdrawing anion comprises sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, or combinations thereof.

A thirteenth embodiment, which is the composition of the ninthembodiment wherein the metal alkyl comprises trialkylaluminum, analkylaluminum halide, an alkylaluminum alkoxide, an aluminoxane, orcombinations thereof.

A fourteenth embodiment, which is the composition of the ninthembodiment wherein the metal alkyl comprises methyl lithium, n-butyllithium, sec-butyl lithium, tert-butyl lithium, diethyl magnesium,di-n-butylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride,diethyl zinc, trimethylaluminum, triethylaluminum, tripropylaluminum,tributylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminumchloride, diethylaluminum bromide, ethylaluminum dichloride,ethylaluminum sesquichloride, methylaluminoxane (MAO), ethylaluminoxane,modified methylaluminoxane (MMAO), n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane,iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane,neopentylaluminoxane, borates, or combinations thereof.

A fifteenth embodiment, which is a polymerization process comprising:

-   -   contacting the catalyst composition of claim 9 with an olefin        monomer and optionally an olefin comonomer under conditions        suitable for the formation of a polymer; and    -   recovering the polymer.

A sixteenth embodiment, which is a polymerization process comprisingcontacting a catalyst composition with a monomer under conditionssuitable for the formation of a polymer and recovering the polymer,wherein the catalyst composition comprises a metal salt complex preparedfrom an imine bis(phenol) compound, a metallocene complex, a solidoxide, and an optional metal alkyl and wherein the metal salt complexprepared from an imine bis(phenol) compound has Structure XIV

where M is titanium, zirconium, or hafnium;

Et₂O is optional;

R comprises a halogen, a hydrocarbyl group, or a substituted hydrocarbylgroup; and

R² comprises hydrogen, a halogen, a hydrocarbyl group, or a substitutedhydrocarbyl group.

A seventeenth embodiment, which is the process of the sixteenthembodiment wherein the metallocene compound comprises at least one ofthe compounds of Structures 1-13:

An eighteenth embodiment, which is the process of the sixteenthembodiment wherein the metallocene compound comprises at least one ofthe compounds of Structures 14-29:

A nineteenth embodiment, which is the process of the sixteenth,seventeenth, or eighteenth embodiment wherein the ratio of the metalsalt complex prepared from an imine bis(phenol) compound to metallocenecomplex is from about 100:1 to about 1:100.

A twentieth embodiment, which is the process of the sixteenth,seventeenth, eighteenth, or nineteenth embodiment wherein the monomercomprises ethylene and the polymer comprises polyethylene.

While embodiments of the disclosure have been shown and described,modifications thereof can be made by one skilled in the art withoutdeparting from the spirit and teachings of the disclosure. Theembodiments described herein are exemplary only, and are not intended tobe limiting. Many variations and modifications of the disclosuredisclosed herein are possible and are within the scope of thedisclosure. Where numerical ranges or limitations are expressly stated,such express ranges or limitations should be understood to includeiterative ranges or limitations of like magnitude falling within theexpressly stated ranges or limitations (e.g., from about 1 to about 10includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11, 0.12, 0.13,etc.). For example, whenever a numerical range with a lower limit, Rl,and an upper limit, Ru, is disclosed, any number falling within therange is specifically disclosed. In particular, the following numberswithin the range are specifically disclosed: R=Rl+k*(Ru−Rl), wherein kis a variable ranging from 1 percent to 100 percent with a 1 percentincrement, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5percent, . . . , 50 percent, 51 percent, 52 percent, . . . , 95 percent,96 percent, 97 percent, 98 percent, 99 percent, or 100 percent.Moreover, any numerical range defined by two R numbers as defined in theabove is also specifically disclosed. Use of the term “optionally” withrespect to any element of a claim is intended to mean that the subjectelement is required, or alternatively, is not required. Bothalternatives are intended to be within the scope of the claim. Use ofbroader terms such as comprises, includes, having, etc. should beunderstood to provide support for narrower terms such as consisting of,consisting essentially of, comprised substantially of, etc.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present disclosure. Thus, the claims are a further description andare an addition to the embodiments of the present disclosure. Thediscussion of a reference herein is not an admission that it is priorart to the present disclosure, especially any reference that may have apublication date after the priority date of this application. Thedisclosures of all patents, patent applications, and publications citedherein are hereby incorporated by reference, to the extent that theyprovide exemplary, procedural, or other details supplementary to thoseset forth herein.

What is claimed is:
 1. A catalyst composition comprising: (i) a metalsalt complex prepared from an imine phenol compound characterized byStructure I:

wherein: O and N represent oxygen and nitrogen respectively; R is ahalogen, a hydrocarbyl group, or a substituted hydrocarbyl group; R² andR³ are each independently hydrogen, a halogen, a hydrocarbyl group, or asubstituted hydrocarbyl group; and Q is a donor group; and (ii) ametallocene complex.
 2. The composition of claim 1 wherein the metalsalt complex prepared from an imine phenol compound has Structure XIV:

where M is a Group 3 to Group 12 transition metal or lanthanide, Et₂O isoptional; and R and R² are each independently hydrogen, a halogen, ahydrocarbyl group, or a substituted hydrocarbyl group.
 3. Thecomposition of claim 1 wherein the metal salt complex prepared from animine phenol compound has structure X:

where Et₂O is optional.
 4. The composition of claim 1 wherein themetallocene compound is represented by a compound having general Formula1 or Formula 2:

where each X is independently F, Cl, Br, I, methyl, benzyl, phenyl, H,BH₄, a hydrocarbyloxide group having up to 20 carbon atoms, ahydrocarbylamino group having up to 20 carbon atoms, atrihydrocarbylsilyl group having up to 20 carbon atoms, OBR′₂ wherein R′is an alkyl group having up to 12 carbon atoms or an aryl group havingup to 12 carbon atoms, and SO₃R″, wherein R″ is an alkyl group having upto 12 carbon atoms or an aryl group having up to 12 carbon atoms; Y is aCR₂ or SiR₂ group where R is hydrogen or a hydrocarbyl group; Cp^(A),Cp^(B), Cp^(C), and Cp^(D) are each independently a substituted orunsubstituted cyclopentadienyl group, indenyl group, or flourenyl groupand where any substituent on Cp^(A), Cp^(B), Cp^(C), and Cp^(D) is H, ahydrocarbyl group having up to 18 carbon atoms or a hydrocarbylsilylgroup having up to 18 carbon atoms.
 5. The composition of claim 1wherein the metallocene compound comprises at least one of the compoundsof Structures 1-13:


6. The composition of claim 1 wherein the metallocene compound isrepresented by a compound having general Formula 3 or Formula 4:

where M is Ti, Zr or Hf; each X is independently F, Cl, Br, I, methyl,phenyl, benzyl, H, BH₄, a hydrocarbyloxide group having up to 20 carbonatoms, a hydrocarbylamino group having up to 20 carbon atoms, atrihydrocarbylsilyl group having up to 20 carbon atoms, OBR′₂ wherein R′is an alkyl group having up to 12 carbon atoms or an aryl group havingup to 12 carbon atoms, or SO₃R″ wherein R″ is an alkyl group having upto 12 carbon atoms or an aryl group having up to 12 carbon atoms; Y is aCR₂, SiR₂, or R₂CCR₂ group which may be linear or cyclic and where R ishydrogen or a hydrocarbyl group; Cp^(A), Cp^(B), Cp^(C), and Cp^(D) areeach independently a substituted or unsubstituted cyclopentadienylgroup, indenyl group, or flourenyl group and where any substituent onCp^(A), Cp^(B), Cp^(C), and Cp^(D) is H, a hydrocarbyl group having upto 18 carbon atoms or a hydrocarbylsilyl group having up to 18 carbonatoms, E represents a bridging group comprising (i) a cyclic orheterocyclic moiety having up to 18 carbon atoms, (ii) a grouprepresented by the general formula E^(A)R^(3A)R^(4A), wherein E^(A) is Cor Si, and R^(3A) and R^(4A) are independently H or a hydrocarbyl grouphaving up to 18 carbon atoms, (iii) a group represented by the generalformula —CR^(3B)R^(4B)—CR^(3C)R^(4C)—, wherein R^(3B), R^(4B), R^(3C),and R^(4C) are independently H or a hydrocarbyl group having up to 10carbon atoms, or (iv) a group represented by the general formula—SiR^(3D)R^(4D)—SiR^(3E)R^(4E)—, wherein R^(3D), R^(4D), R^(3E), andR^(4E) are independently H or a hydrocarbyl group having up to 10 carbonatoms, and wherein at least one of R^(3A), R^(3B), R^(4A), R^(4B),R^(3C), R^(4C), R^(3D), R^(4D), R^(3E), R^(4E), or the substituent onCp, Cp₁, or Cp₂, is (1) a terminal alkenyl group having up to 12 carbonatoms or (2) a dinuclear compound wherein each metal moiety has the samestructural characteristic.
 7. The composition of claim 1 wherein themetallocene compound comprises at least one of the compounds ofStructures 14-29:


8. The composition of claim 1 wherein the metal salt complex preparedfrom an imine phenol compound and the metallocene complex are present inan amount of from about 100:1 to about 1:100 based on the total weightof the catalyst composition.
 9. The composition of claim 1 furthercomprising a metal alkyl compound.
 10. The composition of claim 9,wherein the metal alkyl compound comprises an organoaluminum compound,an aluminoxane compound, and organoboron or organoborate compound, anionizing ionic compound, or combinations thereof.
 11. The composition ofclaim 1, further comprising an activator-support comprising a solidoxide treated with an electron-withdrawing anion.
 12. The composition ofclaim 11 wherein the solid oxide comprises silica, alumina,silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, a mixed oxide thereof, or combinations thereof; andthe electron-withdrawing anion comprises sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, or combinations thereof.
 13. Thecomposition of claim 9 wherein the metal alkyl comprisestrialkylaluminum, an alkylaluminum halide, an alkylaluminum alkoxide, analuminoxane, or combinations thereof.
 14. The composition of claim 9wherein the metal alkyl comprises methyl lithium, n-butyl lithium,sec-butyl lithium, tert-butyl lithium, diethyl magnesium,di-n-butylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride,diethyl zinc, trimethylaluminum, triethylaluminum, tripropylaluminum,tributylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminumchloride, diethylaluminum bromide, ethylaluminum dichloride,ethylaluminum sesquichloride, methylaluminoxane (MAO), ethylaluminoxane,modified methylaluminoxane (MMAO), n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane,iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane,neopentylaluminoxane, borates, or combinations thereof.
 15. Apolymerization process comprising: contacting the catalyst compositionof claim 9 with an olefin monomer and optionally an olefin comonomerunder conditions suitable for the formation of a polymer; and recoveringthe polymer.
 16. A polymerization process comprising contacting acatalyst composition with a monomer under conditions suitable for theformation of a polymer and recovering the polymer, wherein the catalystcomposition comprises a metal salt complex prepared from an iminebis(phenol) compound, a metallocene complex, a solid oxide, and anoptional metal alkyl and wherein the metal salt complex prepared from animine bis(phenol) compound has Structure XIV

where M is titanium, zirconium, or hafnium; Et₂O is optional; Rcomprises a halogen, a hydrocarbyl group, or a substituted hydrocarbylgroup; and R² comprises hydrogen, a halogen, a hydrocarbyl group, or asubstituted hydrocarbyl group.
 17. The process of claim 16 wherein themetallocene compound comprises at least one of the compounds ofStructures 1-13:


18. The process of claim 16 wherein the metallocene compound comprisesat least one of the compounds of Structures 14-29:


19. The process of claim 16 wherein the ratio of the metal salt complexprepared from an imine bis(phenol) compound to metallocene complex isfrom about 100:1 to about 1:100.
 20. The process of claim 16 wherein themonomer comprises ethylene and the polymer comprises polyethylene.